The Eu3+ doped luminescent hydroxyapatite (HAp) nanorods with uniform size and morphology can be synthesized by hydrothermal route. However, these HAp nanorods are coated by hydrophobic oleylamine, which makes them difficult to be dispersed in aqueous solution and impede their biomedical applications. In this work, Eu3+ doped luminescent polymers functionalized HAp nanorods were prepared through the combination of ligand exchange reaction and metal free surface initiated atom transfer radical polymerization (ATRP) method. In this procedure, the amino group functionalized HAp nanorods were first prepared by ligand exchange reaction using adenosine monophosphate (AMP) as ligand. Then the Br-containing initiators (HAp-Br) were introduced onto the surface of HAp-AMP nanorods through the amidation reaction. Finally, polymers functionalized HAp nanorods were prepared by metal free ATRP method using poly(ethylene glycol) methacrylate (PEGMA) as monomer and 10-phenylphenothiazine (PTH) as organic photocatalyst. The properties of these obtained HAp nanocomposites (HAP-polyPEGMA nanorods) were characterized by means of transmission electron microscopy, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis in detail. The cell imaging of these HAP-polyPEGMA nanorods was examined using laser scanning confocal microscope to evaluate their biomedical applications. We demonstrated for the first time that hydrophobic luminescent HAp nanorods can be functionalized with polyPEGMA through the combination of ligand exchange reaction and metal free surface initiated ATRP. As compared with the traditional ATRP, the metal free ATRP can overcome the toxic and fluorescence quenching effects of metal catalysts such as copper ions. More importantly, the strategy described in this work should also be utilized for fabrications of many other luminescent polymer nanocomposites due to its good monomer adoptability.

Ag-doped ZnO nanorods were grown on stainless-steel wire meshes to fabricate the hierarchical photocatalysts with excellent visible light driven activity and anti-photocorrosion property. Effects of Ag doping and the surface structure on the surface chemistry, surface wetting properties, absorption band shift, photoelectrochemical response, and photocatalytic decolorization properties of the hierarchical photocatalysts, together with the stability of photocatalytic activity for recycled photocatalysts were investigated. Ag doping leads to red-shift in the absorption band and increased visible light absorption. Nanorods coated wire meshes hierarchical structure not only increases the surface area of photocatalysts but also makes the surface hydrophilic. The photocatalytic activity enhancement and reduced photocorrosion can be achieved because of increased surface area, enhanced hydrophilicity, and the interaction between the metal wire/ZnO and Ag/ZnO heterostructure interface which can improve the charge separation of photogenerated charge carriers.

Introducing a hydrophobic property to vertically aligned hydrophilic metallicnanorods was investigated experimentally and theoretically. The platinum nanorod arrays were deposited on flat silicon substrates using a sputter glancing angle deposition technique (GLAD). Then a thin layer of Teflon (nanopatch) was partially deposited on the tips of platinum nanorods at a glancing angle of theta(dep) = 85 degrees for different deposition times. Teflon deposition on Pt nanorods at normal incidence (theta(dep) = 0 degrees) was also performed for comparison. Morphology and elemental analysis of Pt/Teflon nanocomposite structures were carried out using scanning electron microscopy (SEM) and energy dispersive x-ray analysis (EDAX), respectively. It was found that the GLAD technique is capable of depositing ultrathin isolated Teflon nanostructures on selective regions of nanorod arrays due to the shadowing effect during obliquely incident deposition. Contact angle measurements on nanocomposite Pt nanorods with Teflon nanopatches exhibited contact angle values as high as 138 degrees, indicating a significant increase in the hydrophobicity of originally hydrophilic Pt nanostructures that had an angle of about 52 degrees. The enhanced hydrophobicity of the Pt nanorod/Teflon nanopatch composite is attributed to the presence of nanostructured Teflon coating, which imparted a low surface energy. Surface energy calculations were performed on Pt nanorods, Teflon thin film, and Pt/Teflon composite using the two-liquid method to confirm the contact angle measurements. Furthermore, a new contact angle model utilizing Cassie and Baxter theory for heterogeneous surfaces was developed in order to explain the enhanced hydrophobicity of Pt/Teflon nanorods. According to our model, it is predicted that the solid-liquid interface is mainly at the Teflon tips when the composite nanorods are in contact with water.

Introducing a hydrophobic property to vertically aligned hydrophilic metallicnanorods was investigated experimentally and theoretically. The platinum nanorod arrays were deposited on flat silicon substrates using a sputter glancing angle deposition technique (GLAD). Then a thin layer of Teflon (nanopatch) was partially deposited on the tips of platinum nanorods at a glancing angle of θdep = 85° for different deposition times. Teflon deposition on Pt nanorods at normal incidence (θdep = 0°) was also performed for comparison. Morphology and elemental analysis of Pt/Teflon nanocomposite structures were carried out using scanning electron microscopy (SEM) and energy dispersive x-ray analysis (EDAX), respectively. It was found that the GLAD technique is capable of depositing ultrathin isolated Teflon nanostructures on selective regions of nanorod arrays due to the shadowing effect during obliquely incident deposition. Contact angle measurements on nanocomposite Pt nanorods with Teflon nanopatches exhibited contact angle values as high as 138°, indicating a significant increase in the hydrophobicity of originally hydrophilic Pt nanostructures that had an angle of about 52°. The enhanced hydrophobicity of the Pt nanorod/Teflon nanopatch composite is attributed to the presence of nanostructured Teflon coating, which imparted a low surface energy. Surface energy calculations were performed on Pt nanorods, Teflon thin film, and Pt/Teflon composite using the two-liquid method to confirm the contact angle measurements. Furthermore, a new contact angle model utilizing Cassie and Baxter theory for heterogeneous surfaces was developed in order to explain the enhanced hydrophobicity of Pt/Teflon nanorods. According to our model, it is predicted that the solid-liquid interface is mainly at the Teflon tips when the composite nanorods are in contact with water.

Undoped and alkali metal i.e Ni doped CdS nanorods (Cd{sub x}Ni{sub 1-x}S) with (x = 0.0, 0.3,) has been synthesized by using a convenient solvothermal technique. In order to confirm the structure of the synthesized nanorods X-ray diffraction (XRD) has been done which reveals the formation of hexagonal phase of the dilute magnetic semiconducting nanorods having size of undoped 27.79nm and doped 17.49nm. Energy dispersive X-ray analysis depicts the presence of elements Cd, Ni and S in their stoichiometric ratio. Optical behavior of undoped and dopednanorods has been investigated. UV-visible spectra show the blue shift in the band gap, as compared to the bulk CdS which may be due the quantum confinement occurs in the nanostructures. Morphological analysis has been done with the help of Transmission electron microscope which confirms the polycrystalline nature of the synthesized nanorods.

In this report we have investigated the optical, electrical and dielectric properties of HCl doped polyaniline nanorods synthesized by the interfacial polymerization technique. High resolution transmission electron microscope (HRTEM) micrographs confirm the formation of nanorods. X-ray diffraction pattern shows the semicrystalline nature of polyaniline nanorods with a diameter distribution in the range of 10-22 nm. The chemical and electronic structures of the polyaniline nanorods are investigated by micro-Raman and UV-vis spectroscopy. Dielectric relaxation spectroscopy has been applied to study the dielectric permittivity, modulus formalism and ac conductivity as a function of frequency and temperature. The ac conductivity follows a power law with frequency. The variation of frequency exponent with temperature suggests that the correlated barrier hopping is the dominant charge transport mechanism. The existence of both polaron and bipolaron in the transport mechanism has been confirmed from the binding energy calculations.

Fluorescence based detection is a commonly used methodology in biotechnology and medical diagnostics. Metalenhanced fluorescence (MEF) becomes a promising strategy to improve the sensitivity of fluorescence detection, where fluorophores coupling with surface plasmon on metallic structures results fluorescence enhancement. To apply the MEF methodology in real medical diagnostics, especially for protein or DNA microarray detection, a large area (e.g., slide glass, 75 × 25 mm2) with uniform metallic nanostructures is required. In this study, we fabricated a large area MEF substrates using oblique angle deposition (OAD), which is a single step, inexpensive large area fabrication method of nanostructures. To optimize the morphological effect, Ag-nanorods with various lengths were fabricated on the conventional slide glass substrates. Streptavidin-Cy5 dissolved in buffer solution with different concentration (100ng/ml 100μg/ml) were applied to MEF substrates using a pipette, and the fluorescence signals were measured. The enhancement factor increased with the increase in length of Ag-nanorods and maximum enhancement factor 91x was obtained from Ag-nanorods 750nm length compare to bare glass due to higher surface Plasmon effect.

In this Feature Article, we examine recent advances in chemical analyte detection and optical imaging applications using gold and silver nanoparticles, with a primary focus on our own work. Noble metal nanoparticles have exciting physical and chemical properties that are entirely different from the bulk. For chemical sensing and imaging, the optical properties of metallic nanoparticles provide a wide range of opportunities, all of which ultimately arise from the collective oscillations of conduction band electrons ("plasmons") in response to external electromagnetic radiation. Nanorods have multiple plasmon bands compared to nanospheres. We identify four optical sensing and imaging modalities for metallic nanoparticles: (1) aggregation-dependent shifts in plasmon frequency; (2) local refractive index-dependent shifts in plasmon frequency; (3) inelastic (surface-enhanced Raman) light scattering; and (4) elastic (Rayleigh) light scattering. The surface chemistry of the nanoparticles must be tunable to create chemical specificity, and is a key requirement for successful sensing and imaging platforms.

We report a general method for the synthesis of noble metalnanorods, including Au, Ag, Pt, and Pd, based on their seeded growth in silica nanotube templates. The controlled growth of the metals occurs exclusively on the seeds inside the silica nanotubes, which act as hard templates to confine the one-dimensional growth of the metalnanorods and define their aspect ratios. This method affords large quantities of noble metalnanorods with well-controlled aspect ratios and high yield, which may find wide use in the fields of nanophotonics, catalysis, sensing, imaging, and biomedicine.

We report on structural and optical changes induced by impurity incorporation in ZnO nanorods grown via electrodeposition. We find the lattice parameters of the hexagonal ZnO rods to be larger than in defect-free single-crystalline ZnO. SIMS measurements indicate impurity incorporation and doping in the bulk of the nanorods. The impurity content correlates with changes in the electroluminescence spectra. The maximum of the defect luminescence band around 600 nm shifts towards longer wavelengths with metal incorporation. Aluminum incorporation leads to a narrow luminescence band close by the bandgap of ZnO around 390 nm.

ZnS nanorodsdoped with 0-15 mol% of Cu have been prepared by simple solvothermal process. With gradual increase in the Cu concentration, phase transformation of the doped ZnS nanorods from wurtzite to cubic was observed. Twins and stacking faults were developed due to atomic rearrangement in the heavily doped ZnS nanorods during phase transformation. UV-vis-NIR absorbance spectroscopy ruled out the presence of any impure Cu-S phase. The doped ZnS nanorods showed luminescence over a wide range from UV to near IR with peaks at 370, 492-498, 565 and 730 nm. The UV region peak is due to the near-band-edge transition, whereas, the green peak can be related to emission from elementary sulfur species on the surfaces of the nanorods. The orange emission at 565 nm may be linked to the recombination of electrons at deep defect levels and the Cu(t{sub 2}) states present near the valence band of ZnS. The near IR emission possibly originated from transitions due to deep-level defects. - Graphical abstract: ZnS nanorodsdoped with 0-15 mol% of Cu has been prepared by simple solvothermal route. Interestingly, phase transformation of the doped ZnS nanorods from wurtzite to cubic was observed with gradual increase in the Cu concentration. Doped ZnS nanorods showed luminescence over a wide range from UV to near IR, which is also a rare observation.

Yttrium-doped ZnO nanorod arrays were applied to photoanodes of quantum dot-sensitized solar cells (QDSCs). The introduction of yttrium to ZnO nanostructures facilitates the growth of ZnO nanorods and increases the amount of QD deposition with a large surface area. Furthermore, lower electrical resistance and longer electron lifetime were achieved with yttrium-doping owing to fewer defects and trap sites on the surface of yttrium-doped ZnO nanorods. As a result, the conversion efficiency of 3.3% was achieved with the optimized concentration of yttrium.

The many millions of organic, inorganic, and bioorganic molecules represent a very rich library of chemical, biological, and physical properties that do not show up among the approximately 100 metals. The ability to imbue metals with any of these molecular properties would open up tremendous potential for the development of new materials. In addition to their traditional features and their traditional applications, metals would have new traits, which would merge their classical virtues such as conductivity and catalytic activity with the diverse properties of these molecules. In this Account, we describe a new materials methodology, which enables, for the first time, the incorporation and entrapment of small organic molecules, polymers, and biomolecules within metals. These new materials are denoted dopant@metal. The creation of dopant@metal yields new properties that are more than or different from the sum of the individual properties of the two components. So far we have developed methods for the doping of silver, copper, gold, iron, palladium, platinum, and some of their alloys, as well as Hg-Ag amalgams. We have successfully altered classical metal properties (such as conductivity), induced unorthodox properties (such as rendering a metal acidic or basic), used metals as heterogeneous matrices for homogeneous catalysts, and formed new metallic catalysts such as metalsdoped with organometallic complexes. In addition, we have created materials that straddle the border between polymers and metals, we have entrapped enzymes to form bioactive metals, we have induced chirality within metals, we have made corrosion-resistant iron, we formed efficient biocidal materials, and we demonstrated a new concept for batteries. We have developed a variety of methods for synthesizing dopant@metals including aqueous homogeneous and heterogeneous reductions of the metal cations, reductions in DMF, electrochemical entrapments, thermal decompositions of zerovalent metal carbonyls

The optical transmission spectra, the photoluminescence (PL), and the photoluminescence excitation (PLE) spectra of the cobalt doped zinc oxide nanorods Zn1-xCoxO (x = 0.01, 0.10) were measured by Loan et al. [J. Phys. D: Appl. Phys. 42, 065412 (2009)] in the region 1.5-4 eV. These spectra exhibit a group of ultraviolet narrow lines in the region of 3.0-3.4 eV related to the near-band-edge emission of the host ZnO materials and a group of emission lines in the red region of 1.8-1.9 eV assigned to the radiative transitions within the tetrahedral Co2+ ions in the ZnO host crystal. The group of lines in the visible region provides important information about the electronic structure of the cobalt doped zinc oxide nanorods. This work investigates a theoretical crystal-field analysis of the visible lines associated to the Co2+ ion transition occupying a Td site symmetry in ZnO host crystal. A satisfactory correlations were obtained between experimental and calculated energy levels. The electronic structure was compared with the reported for cobalt transition ion doped in ZnO nanoparticles and bulk crystals [Volbers et al., Appl. Phys. A 88, 153 (2007) and H. J. Schulz and M. Thiede, Phys. Rev. B 35, 18 (1987)]. In order to explain the existence of excitation peaks observed near the band edge of the ZnO host, an energy transfer mechanism is proposed.

Nanomaterials research has become a major attraction in the field of advanced materials research in the area of Physics, Chemistry, and Materials Science. Bio-compatible and chemically stable metal nanoparticles have biomedical applications that includes drug delivery, cell and DNA separation, gene cloning, magnetic resonance imaging (MRI). This research is aimed at the fabrication and characterization of Mg-doped ZnO nanorods. Hydrothermal synthesis of undoped ZnO and Mg-doped ZnO nanorods is carried out using aqueous solutions of Zn(NO3)2 .6H2O, MgSO4, and using NH4OH as hydrolytic catalyst. Nanomaterials of different sizes and shapes were synthesized by varying the process parameters such as molarity (0.15M, 0.3M, 0.5M) and pH (8-11) of the precursors, growth temperature (130°C), and annealing time during the hydrothermal Process. Structural, morphological, and optical properties are studied using various techniques such as XRD, SEM, UV-vis and PL spectroscopy. Detailed structural, and optical properties will be discussed in this presentation. This work is partially supported by National Cancer Institute (1 R15 CA139390-01).

One dimensional uniform Sm{sup 3+} doped gadolinium hydroxide nanorods have been prepared via simple co– precipitation technique at 60 °C temperature for 1 hour. The samples were calcinated at 750 °C to obtain Sm{sup 3+} doped gadolinium oxide nanorods. The 1D nanorods were then subjected to different characterization techniques to ascertain its structural stability and its morphology were investigated using high–resolution transmission electron microscopy. Photoluminescence (PL) spectrophotometry was investigated and the obtained results were discussed in detail.

Samarium doped ZnO nanorods were grown on silicon substrate by using vapor phase transport method (VPT) with the growth temperature of 950°C. The synthesized nanorods were characterized by XRD, field emission scanning electron microscopy, Raman spectra, and photocurrent measurements. The XRD result revealed that Sm was successfully doped into lattice plane of hexagonal ZnO nanorods. The FESEM result confirms the pure ZnO has nanorod like morphology with an average diameter and length of 130nm and 10µm respectively. The above observation is supported by the Micro-Raman spectroscopy result. The photocurrent in the visible region has been significantly enhanced due to deposition of Sm on the surface of the ZnO nanorods. Sm acts as a visible sensitizer because of its lower band gap compared to ZnO.

Cu-doped ZnO nanorods have been grown at 90°C for 90 min onto a quartz substrate pre-coated with a ZnO seed layer using a hydrothermal method. The influence of copper (Cu) precursor and concentration on the structural, morphological, and optical properties of ZnO nanorods was investigated. X-ray diffraction analysis revealed that the nanorods grown are highly crystalline with a hexagonal wurtzite crystal structure grown along the c-axis. The lattice strain is found to be compressive for all samples, where a minimum compressive strain of −0.114% was obtained when 1 at.% Cu was added from Cu(NO3)2. Scanning electron microscopy was used to investigate morphologies and the diameters of the grown nanorods. The morphological properties of the Cu-doped ZnO nanorods were influenced significantly by the presence of Cu impurities. Near-band edge (NBE) and a broad blue-green emission bands at around 378 and 545 nm, respectively, were observed in the photoluminescence spectra for all samples. The transmittance characteristics showed a slight increase in the visible range, where the total transmittance increased from approximately 80% for the nanorodsdoped with Cu(CH3COO)2 to approximately 90% for the nanorods that were doped with Cu(NO3)2. PMID:24855460

We synthesized one-dimensional (1D) Magnéli-phase nanorods of Mo4O11 using the hot filament metal-oxide vapor deposition technique. The 1D Magnéli-phase Mo4O11 nanorods synthesized at 1000, 1050, 1100, 1150, and 1200 °C contain varying combinations of two orthorhombic (α) and monoclinic (η) phases, and various mixtures of Mo(4+), Mo(5+) and Mo(6+) cations, while those synthesized at a higher temperature look bluer. The shifts of the transmittance maximum and absorbance minimum of the 1D Magnéli-phase Mo4O11 nanorods are inversely and linearly proportional to the elevated temperature, verifying that the bandgaps (Eg) are inversely proportional to the elevated temperature. The bandgap (Eg) of the 1D Magnéli-phase Mo4O11 nanorods can be tuned by simply controlling the synthesis temperature without doping with other materials, giving the 1D Magnéli-phase Mo4O11 nanorods good potential for use in optoelectronic nanodevices and bandgap engineering.

Metal enhanced fluorescence of Oxazine720 fluorophore with gold and gold/silver core-shell nanorods is investigated experimentally in aqueous solution system. Metallicnanorods are synthesized for providing proper localized surface plasmon resonance and necessary enhancement to the fluorophore molecule. The experimental observation shows that the fluorescence enhancement increases firstly and then decreases when the concentration of metallicnanorods increases, which is resulted by the competition between enhanced emission and inner-filtering effect. Further investigation with different amounts of metallicnanorods shows that the relationship between metal enhanced fluorescence and spectral correlation strongly depends on the concentration of metallicnanorods.

In this work, tunable wettability of the Zinc Oxide (ZnO) nanorod surface with Cu doping prepared by a hydrothermal method. These grown samples were characterized by XRD, FESEM, AFM and water contact angle measurements. The wettability of the ZnO nanorods surface area was controlled and tuned by different concentration of copper doping. It was found that the hydrophobic surface of doped ZnO Nanorods shows a maximum and minimum contact angle of about 156.60° and 136.36° was achieved with doping concentration of 10 and 20 M % respectively. Further, the surface properties such as surface energy and work of adhesion were calculated for undoped and Cu doped ZnO nanostructure surfaces. These nanosructures can be potentially applicable to enlarge time honoured application of ZnO based electronic devices.

The authors attempted to fabricate and characterize one dimensional metal-semiconductor-metal (MSM) nanorod using a template. Cadmium selenide (CdSe) and polypyrrole (Ppy) were chosen as n-type and p-type semiconductor materials, respectively, whereas Au was chosen as a metal electrode. The fabrication of the nanorod was achieved by ''template synthesis'' method using polycarbonate membrane. The structure of the fabricated nanorod was analyzed using scanning electron microscopy and energy dispersive spectroscopy. In addition, the electrical properties of MSM nanorods were characterized using scanning probe microscopy (Seiko Instruments, SPA 300 HV) by probing with a conductive cantilever. I-V characteristics as a function of the temperature give the activation energy, as well as the barrier height of a metal-semiconductor contact, which is useful to understand the conduction mechanism of MSM nanorods.

Growth of metallicnanorods by physical vapor deposition is a common practice, and the origin of their dimensions is a characteristic length scale that depends on the three-dimensional Ehrlich-Schwoebel (3D ES) barrier. For most metals, the 3D ES barrier is large so the characteristic length scale is on the order of 200 nm. Using density functional theory-based ab initio calculations, this paper reports that the 3D ES barrier of Al is small, making it infeasible to grow Al nanorods. By analyzing electron density distributions, this paper shows that the small barrier is the result of covalent bonding in Al. Beyond the infeasibility of growing Al nanorods by physical vapor deposition, the results of this paper suggest a new mechanism of controlling the 3D ES barrier and thereby nanorod growth. The modification of local degree of covalent bonding, for example, via the introduction of surfactants, can increase the 3D ES barrier and promote nanorod growth, or decrease the 3D ES barrier and promote thin film growth.

We have fabricated, characterized, and compared ZnO nanorods/p-GaN and n-Zn0.94Ag0.06O nanorods/p-GaN light emitting diodes (LEDs). Current-voltage measurement showed an obvious rectifying behaviour of both LEDs. A reduction of the optical band gap of the Zn0.94Ag0.06O nanorods compared to pure ZnO nanorods was observed. This reduction leads to decrease the valence band offset at n-Zn0.94Ag0.06O nanorods/p-GaN interface compared to n-ZnO nanorods/p-GaN heterojunction. Consequently, this reduction leads to increase the hole injection from the GaN to the ZnO. From electroluminescence measurement, white light was observed for the n-Zn0.94Ag0.06O nanorods/p-GaN heterojunction LEDs under forward bias, while for the reverse bias, blue light was observed. While for the n-ZnO nanorods/p-GaN blue light dominated the emission in both forward and reverse biases. Further, the LEDs exhibited a high sensitivity in responding to UV illumination. The results presented here indicate that doping ZnO nanorods might pave the way to tune the light emission from n-ZnO/p-GaN LEDs.

The design and synthesis of multifunctional systems with high biocompatibility are very significant for the future of clinical applications. Herein, we report a microwave-assisted rapid synthesis of multifunctional Eu(3+)/Gd(3+) dual-doped hydroxyapatite (HAp) nanorods, and the photoluminescence (PL), drug delivery and in vivo imaging of as-prepared Eu(3+)/Gd(3+) doped HAp nanorods. The photoluminescent and magnetic multifunctions of HAp nanorods are realized by the dual-doping with Eu(3+) and Gd(3+). The PL intensity of doped HAp nanorods can be adjusted by varying Eu(3+) and Gd(3+) concentrations. The magnetization of doped HAp nanorods increases with the concentration of doped Gd(3+). The as-prepared Eu(3+)/Gd(3+)-doped HAp nanorods exhibit inappreciable toxicity to the cells in vitro. More importantly, the Eu(3+)/Gd(3+)-doped HAp nanorods show a high drug adsorption capacity and sustained drug release using ibuprofen as a model drug, and the drug release is governed by a diffusion process. Furthermore, the noninvasive visualization of nude mice with subcutaneous injection indicates that the Eu(3+)/Gd(3+)-doped HAp nanorods with the photoluminescent function are suitable for in vivo imaging. In vitro and in vivo imaging tests indicate that Eu(3+)/Gd(3+)-doped HAp nanorods have a potential in applications such as a multiple-model imaging agent for magnetic resonance (MR) imaging, photoluminescence imaging and computed tomography (CT) imaging. The Eu(3+)/Gd(3+) dual-doped HAp nanorods are promising for applications in the biomedical fields such as multifunctional drug delivery systems with imaging guidance.

A two-step method is adopted to synthesize Ag-doped ZnO nanorods. A ZnO seed layer is first prepared on a glass substrate by thermal decomposition of zinc acetate. Ag-doped ZnO nanorods are then assembled on the ZnO seed layer using the hydrothermal method. The influences of the molar percentage of Ag ions to Zn ions (RAg/Zn) on the structural and optical properties of the ZnO nanorods obtained are carefully studied using X-ray diffractometry, scanning electron microscopy and spectrophotometry. Results indicate that Ag ions enter into the crystal lattice through the substitution of Zn ions. The (002) c-axis-preferred orientation of the ZnO nanorods decreases as RAg/Zn increases. At RAg/Zn > 1.0%, ZnO nanorods lose their c-axis-preferred orientation and generate Ag precipitates from the ZnO crystal lattice. The average transmissivity in the visible region first increases and then decreases as RAg/Zn increases. The absorption edge is first blue shifted and then red shifted. The influence of Ag doping on the average head face, and axial dimensions of the ZnO nanorods may be optimized to improve the average transmissivity at RAg/Zn < 1.0%.

One-dimensional nitride based diluted magnetic semiconductors were grown by plasma-assisted molecular beam epitaxy. Delta-doping technique was adopted to dope GaN nanorods with Mn. The structural and magnetic properties were investigated. The GaMnN nanorods with a single crystalline structure and with Ga sites substituted by Mn atoms were verified by high-resolution x-ray diffraction and Raman scattering, respectively. Secondary phases were not observed by high-resolution x-ray diffraction and high-resolution transmission electron microscopy. In addition, the magnetic hysteresis curves show that the Mn delta-doped GaN nanorods are ferromagnetic above room temperature. The magnetization with magnetic field perpendicular to GaN c-axis saturates easier than the one with field parallel to GaN c-axis.

Al-doped ZnO (AZO) nanorod array thin films with various Al/Zn molar ratios were synthesized by chemical bath deposition. The resultant AZO nanorods were well-aligned at the glass substrate, growing vertically along the c-axis [001] direction. In addition, they had an average diameter of 64.7 +/- 16.8 nm and an average length of about 1.0 microm with the structure of wurtzite-type ZnO. Analyses of energy dispersive x-ray spectra and x-ray photoelectron spectra indicated that Al atoms had been doped into the ZnO crystal lattice. The doping of Al atoms did not result in significant changes in the structure and crystal orientation, but the electrical resistivity was found to increase first and then decrease with increasing Al content owing to the increase of carrier concentration and the decrease of mobility. In addition, the transmission in the visible region increased but the increase was reduced at higher Al doping levels. After hydrogen treatment, the morphology of the AZO nanorod array thin films remained unchanged. However, the electrical resistivity decreased significantly due to the formation of oxygen vacancies and interstitial hydrogen atoms. When the real Al/Zn molar ratio was about 3.7%, the conductivity was enhanced about 1000 times and a minimum electrical resistivity of 6.4 x 10( - 4) Omega cm was obtained. In addition, the transmission of the ZnO nanorod array thin film in the visible region was significantly increased but the increase was less significant for the AZO nanorod array thin film, particularly at higher Al doping levels. In addition, the current-voltage curves of the thin film devices with ZnO or AZO nanorod arrays revealed that AZO had a higher current response than ZnO and hydrogen treatment led to a more significant enhancement of current responses (about 100-fold).

Doping elements in hematite nanostructures is a promising approach to improve the photoelectrochemical (PEC) water-splitting performance of hematite photoanodes. However, uniform doping with precise control on doping amount and morphology is the major challenge for quantitatively investigating the PEC water-splitting enhancement. Here, we report on the design and synthesis of uniform titanium (Ti)-doped hematite nanorods with precise control of the Ti amount and morphology for highly effective PEC water splitting using an atomic layer deposition assisted solid-state diffusion method. We found that Ti doping promoted band bending and increased the carrier density as well as the surface state. Remarkably, these uniformly doped hematite nanorods exhibited high PEC performance with a pronounced photocurrent density of 2.28 mA/cm(2) at 1.23 V vs reversible hydrogen electrode (RHE) and 4.18 mA/cm(2) at 1.70 V vs RHE, respectively. Furthermore, as-prepared Ti-doping hematite nanorods performed excellent repeatability and durability; over 80% of the as-fabricated photoanodes reproduced the steady photocurrent density of 1.9-2.2 mA/cm(2) at 1.23 V vs RHE at least 3 h in a strong alkaline electrolyte solution.

Multifunctional colloidal core-shell nanoparticles of magnetic nanocrystals (of iron oxide or FePt) or gold nanorods encapsulated in silica shells doped with the fluorescent dye, Tris(2,2'-bipyridyl)dichlororuthenium(II) hexahydrate (Rubpy) were synthesized. The as-prepared magnetic nanocrystals are initially hydrophobic and were coated with silica using a microemulsion approach, while the as-prepared gold nanorods are hydrophilic and were coated with silica using a Stoeber type of process. Each approach yielded monodisperse nanoparticles with uniform fluorescent dye-doped silica shells. These colloidal heterostructures have the potential to be used as dual-purpose tags-exhibiting a fluorescent signal that could be combined with either dark-field optical contrast (in the case of the gold nanorods), or enhanced contrast in magnetic resonance images (in the case of magnetic nanocrystal cores). The optical and magnetic properties of the fluorescent silica-coated gold nanorods and magnetic nanocrystals are reported. - Graphical abstract: Colloidal gold nanorods and iron platinum and iron oxide nanocrystals were encapsulated with fluorescent dye-doped silica shells using a generic coating strategy. These heterostructures are promising contrast agents for dual-mode medical imaging. Their optical and magnetic properties were studied and are reported here.

Here, synthesis, structural, morphological, Raman, optical properties and antibacterial activity of undoped and Ag doped ZnO nanorods by chemical co-precipitation technique have been reported. Structural analysis has revealed that Ag doping cannot deteriorate the structure of ZnO and wurtzite phase is maintained. Lattice constants are found to be decreased with the Ag doping. Fourier transform infrared and Raman spectroscopy also confirm the X-ray diffraction results. Scanning electron microscopy results have demonstrated the formation of ZnO nanorods with average diameter and length of 96 nm and 700 nm, respectively. Raman spectroscopy results suggest that the Ag doping enhances the number of defects in ZnO crystal. It has been found from optical study that Ag doping results in positional shift of band edge absorption peak. This is attributed to the successful incorporation of Ag dopant into ZnO host matrix. The antibacterial activity of prepared nanorods has been determined by two different methods and compared to that of undoped ZnO nanorods. Ag doped ZnO nanorods exhibit excellent antibacterial activity as compared to that of undoped ZnO nanorods. This excellent antibacterial activity may be attributed to the presence of oxygen vacancies and Zn{sup 2+} interstitial defects. Our preliminary findings suggest that Ag doped ZnO nanorods can be used externally to control the spreading of infections related with tested bacterial strains.

Here, synthesis, structural, morphological, Raman, optical properties and antibacterial activity of undoped and Ag doped ZnO nanorods by chemical co-precipitation technique have been reported. Structural analysis has revealed that Ag doping cannot deteriorate the structure of ZnO and wurtzite phase is maintained. Lattice constants are found to be decreased with the Ag doping. Fourier transform infrared and Raman spectroscopy also confirm the X-ray diffraction results. Scanning electron microscopy results have demonstrated the formation of ZnO nanorods with average diameter and length of 96 nm and 700 nm, respectively. Raman spectroscopy results suggest that the Ag doping enhances the number of defects in ZnO crystal. It has been found from optical study that Ag doping results in positional shift of band edge absorption peak. This is attributed to the successful incorporation of Ag dopant into ZnO host matrix. The antibacterial activity of prepared nanorods has been determined by two different methods and compared to that of undoped ZnO nanorods. Ag doped ZnO nanorods exhibit excellent antibacterial activity as compared to that of undoped ZnO nanorods. This excellent antibacterial activity may be attributed to the presence of oxygen vacancies and Zn2+ interstitial defects. Our preliminary findings suggest that Ag doped ZnO nanorods can be used externally to control the spreading of infections related with tested bacterial strains.

In this paper, a two-step process is developed to synthesize rare earth doped titania nanorods (RE–TiO2 NRs) as photocatalysts for efficient degradation of lignin under simulated sunlight irradiation. In this approach, protonated titanate nanotubes with layered structures were first prepared by a hydrothermal approach, and rare earth metal ions were subsequently bound to the negatively charged surface of the synthesized titanate via electrostatic incorporation. The as-synthesized RE–TiO2 NRs after calcination generally showed much higher photocatalytic efficiencies than those of undoped TiO2 NRs or the commercial P25 TiO2 photocatalyst. Using methyl orange (MO) as a probing molecule, we demonstrate that Eu–TiO2more » NRs are among the best for degrading MO, with an observed rate constant of 4.2 × 10-3 s-1. The La3+, Sm3+, Eu3+ and Er3+ doped TiO2 NRs also showed higher photocatalytic efficiencies in degrading MO than the commercial P25 TiO2. Finally, we further demonstrate that lignin can be photodegraded effectively and rapidly at room temperature under simulated sunlight through two reaction routes, which could be important in controlling ways of lignin depolymerization or the formation of reaction products.« less

We report on field emission property from a single nanorod measured by using scanning tunnelling spectroscopy. It has been shown that field emission from nanorods of small band gap semiconductor is significantly increasing by doping. The current transport mechanism is explained using double barrier tunnel junction formalism. It is observed experimentally that the Fowler-Nordheim tunnelling mechanism is dominant and governs the transport mechanism. The transport properties of PbS nanostructures in the form of nanorod are investigated in terms of various conduction mechanism. The minimum voltage necessary for triggering Fowler-Nordheim tunnelling under the revised biased for intrinsic sample ~0.95 V and decreases to ~0.67 V for increase doping concentration up to 1.76 wt%.

Embodiments of the invention relate to an electrochemical cell comprising: (i) a fuel electrode comprising a metal fuel, (ii) a positive electrode, (iii) an ionically conductive medium, and (iv) a dopant; the electrodes being operable in a discharge mode wherein the metal fuel is oxidized at the fuel electrode and the dopant increases the conductivity of the metal fuel oxidation product. In an embodiment, the oxidation product comprises an oxide of the metal fuel which is doped degenerately. In an embodiment, the positive electrode is an air electrode that absorbs gaseous oxygen, wherein during discharge mode, oxygen is reduced at the air electrode. Embodiments of the invention also relate to methods of producing an electrode comprising a metal and a dopedmetal oxidation product.

Organic foams having a low density and very small cell size and method for producing same in either a metal-loaded or unloaded (nonmetal loaded) form are described. Metal-doped foams are produced by soaking a polymer gel in an aqueous solution of desired metal salt, soaking the gel successively in a solvent series of decreasing polarity to remove water from the gel and replace it with a solvent of lower polarity with each successive solvent in the series being miscible with the solvents on each side and being saturated with the desired metal salt, and removing the last of the solvents from the gel to produce the desired metal-doped foam having desired density cell size, and metal loading. The unloaded or metal-doped foams can be utilized in a variety of applications requiring low density, small cell size foam. For example, rubidium-doped foam made in accordance with the invention has utility in special applications, such as in x-ray lasers.

Herein we have established a strategy for the synthesis of highly luminescent and biocompatible europium-doped lanthanum orthophosphate (La0.85PO4Eu0.15(3+)) nanorods. The structure and morphogenesis of these nanorods have been probed by XRD, SEM, and TEM/HRTEM techniques. The XRD result confirms that the as-synthesized nanorods form in a monazite phase with a monoclinic crystal structure. Furthermore, the surface morphology shows that the synthesized nanorods have an average diameter of ∼90 nm and length of ∼2 μm. The HRTEM images show clear lattice fringes that support the presence of better crystal quality and enhanced photoluminescence hypersensitive red emission at 610 nm ((5)D0-(7)F2) upon 394 nm wavelength excitation. Furthermore, time-resolved spectroscopy and an MTT assay of these luminescent nanorods demonstrate a photoluminescent decay time of milliseconds with nontoxic behavior. Hence, these obtained results suggest that the as-synthesized luminescent nanorods could be potentially used in invisible security ink and high-contrast bioimaging applications.

In this paper, ZnO nanorodsdoped with varying amounts of Ni have been prepared by chemical co-precipitation technique. Structural investigations provide the evidence that Ni is successfully doped into ZnO host matrix without having any secondary phases. Scanning electron microscopy (SEM) images reveal the formation of rodlike structure of undoped ZnO with average length and diameter of 1 μm and 80 nm, respectively. Raman spectroscopy results show that the E1LO phonons mode band shifts to the higher values with Ni doping, which is attributed to large amount of crystal defects. Ni doping is also found to greatly influence the optical properties of ZnO nanorods. The influence of Ni doping on antibacterial characteristics of ZnO nanorods have been studied by measuring the growth curves of Escherichia coli (E. coli), Methicillin-resistant Staphylococcus aureus (S. aureus) and Pseudomonas aeruginosa (P. aeruginosa) bacteria in the presence of prepared nanorods. ZnO nanorods antibacterial potency is found to increase remarkably with Ni doping against S. aureus and P. aeruginosa microbials, which might possibly be due to the increase in reactive oxygen species (ROS) generation. Interestingly, it is observed that Ni doped ZnO nanorods completely eradicates these multi-drug resistant bacteria.

We observe obviously different diffraction efficiencies with forward and reverse dc voltages in a forced-light-scattering (FLS) experiment for a cell with ZnO nanoroddoped in only one poly (vinyl alcohol) (PVA) layer. When a dc voltage with a positive pole on the ZnO nanoroddoped side is applied, the excited charge carriers primarily move along the transverse direction, which results in a higher diffraction efficiency. Conversely, when the dc voltage with a negative pole on the ZnO nanoroddoped side is applied, the excited charge carriers primarily move along the longitudinal direction, which leads to a lower diffraction efficiency. A largest diffraction efficiency of about 9% is achieved in the ZnO nanoroddoped liquid crystal cell.

Multifunctional colloidal core-shell nanoparticles of magnetic nanocrystals (of iron oxide or FePt) or gold nanorods encapsulated in silica shells doped with the fluorescent dye, Tris(2,2′-bipyridyl)dichlororuthenium(II) hexahydrate (Rubpy) were synthesized. The as-prepared magnetic nanocrystals are initially hydrophobic and were coated with silica using a microemulsion approach, while the as-prepared gold nanorods are hydrophilic and were coated with silica using a Stöber-type of process. Each approach yielded monodisperse nanoparticles with uniform fluorescent dye-doped silica shells. These colloidal heterostructures have the potential to be used as dual-purpose tags—exhibiting a fluorescent signal that could be combined with either dark-field optical contrast (in the case of the gold nanorods), or enhanced contrast in magnetic resonance images (in the case of magnetic nanocrystal cores). The optical and magnetic properties of the fluorescent silica-coated gold nanorods and magnetic nanocrystals are reported. PMID:19578476

Cuprous oxide (Cu{sub 2}O) nanorodsdoped with iron impurities have been synthesized by the polyol method using sodium dodecyl sulfate as the surfactant. The X-ray diffraction measurement reveals the pure phase of simple cubic Cu{sub 2}O and the electron microscopy displays its one dimensional morphology. Ferromagnetism was observed at room temperature in the magnetic measurements of the doped samples while undoped sample exhibits only diamagnetism. Room temperature Moessbauer spectra for the samples exhibited only doublets but no sextet, which corresponds to the presence of paramagnetic iron sites. As magnetic moment contribution of the doped ions was insignificant for the observed magnetism, ferromagnetic property in the doped samples could have been originated from the defects as cation vacancies. Existence of the defects was supported by the room temperature photoluminescence spectra of the doped samples in reference to the undoped sample. - Ferromagnetism at room temperature was observed in the Fe doped Cu{sub 2}O nanorods. The origin seems to be the defects of cation vacancies created by the dopant ions.

Nanorods of calcium sulfate (CaSO4) activated by Ag, Cu, Dy, Eu and Tb were synthesized by the co-precipitation technique. They were irradiated by γ-rays in a wide range of exposures and studied for their thermoluminesence (TL) properties. The as-synthesized samples were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and photoluminescence (PL) emission spectra. SEM images show that the samples doped with rare earths elements (i.e. Dy, Eu and Tb) have thinner nanorods than the other samples, while XRD pattern shows a complete crystalline structures in a monoclinic phase. The TL glow curves of these samples show two components. The first one include low temperature glow peaks at around 125 °C, while the second component shows high temperature peaks in the range 230-270 °C. These glow peaks diver from sample to sample by their TL intensity. The TL results are promising, particularly that of Tb and Eu. Tb doped sample is found to be a highly TL sensitive with a prominent glow peak at around 270 °C, while Eu has created very active, high dense electron traps. The later shows quite linear response in the whole studied exposures i.e. 10 Gy-10 kGy. These results show that Eu or Tb doped CaSO4 nanorods might be proper candidates as dosimeters for high doses of ionizing radiations used in irradiation of foods and seeds.

Nanostructured zinc oxide material is usable in electronic device applications such as light-emitting diodes, heterojunction diode, sensors, solar cell due to its interesting electrical conductivity and optical properties. Magnesium-doped zinc oxide nanorod (NR)-nanotube (NT) films were grown by microwave-assisted chemical bath deposition to fabricate ZnO-based heterojunction diode. It is found that ZnO hexagonal nanorods turn into hexagonal nanotubes when the Mg doping ratio is increased from 1 to 10 %. The values of the optical band gap for 1 % Mg-doped ZnO NR and 10 % Mg-doped ZnO NT films are found to be 3.14 and 3.22 eV, respectively. The n-ZnO:Mg/p-Si heterojunction diodes were fabricated. The diodes exhibited a rectification behavior with ideality factor higher than unity due to the presence of surface states in the junction and series resistance. The obtained results indicate that Mg doping improves the electrical and optical properties of ZnO.

Alloyed metalnanorods offer a unique combination of enhanced plasmonic and photothermal properties with a wide variety in optical and catalytic properties as a function of the alloy composition. Here, we show that fully alloyed anisotropic nanoparticles can be obtained with complete retention of the particle shape via thermal treatment at surprisingly low temperatures. By coating Au-Ag, Au-Pd and Au-Pt core-shell nanorods with a protective mesoporous silica shell the transformation of the rods to a more stable spherical shape was successfully prevented during alloying. For the Au-Ag core-shell NRs the chemical stability was drastically increased after alloying, and from Mie-Gans and finite-difference time-domain (FDTD) calculations it followed that alloyed AuAg rods also exhibit much better plasmonic properties than their spherical counterparts. Finally, the generality of our method is demonstrated by alloying Au-Pd and Au-Pt core-shell NRs, whereby the AuPd and AuPt alloyed NRs showed a surprisingly high increase in thermal stability of several hundred degrees compared with monometallic silica coated Au NRs.

La-doped ZnO nanorods with different La contents were synthesized by microwave assisted method and characterized by various sophisticated techniques such as XRD, UV-Vis., EDS, XPS, SEM and TEM. The XRD patterns of the La-doped ZnO indicate hexagonal crystal structure with an average crystallite size of 30nm. It was found that the crystallite size of La-doped ZnO is much smaller as compared to pure ZnO and decreases with increasing La content. The photocatalytic activity of 0.5mol% La-doped ZnO in the degradation of metasystox was studied. It was observed that degradation efficiency of metasystox over La-doped ZnO increases up to 0.5mol% doping then decreases for higher doping levels. Among the catalyst studied, the 0.5mol% La-doped ZnO was the most active, showing high photocatalytic activity for the degradation of metasystox. The maximum reduction of concentration of metasystox was observed under static condition at pH 8. Reduction in the Chemical Oxygen Demand (COD) of metasystox was observed after 150min. The cytotoxicological studies of meristematic root tip cells of Allium cepa were studied. The results obtained indicate that photocatalytically degraded products of metasystox were less toxic as compared to metasystox.

Zn(1-x)Co(x)O (x = 0-0.07) single-crystalline nanorods were prepared by a modified microemulsion route. The crystalline structure, morphology, optical, and hysteresis loop at low and room temperature of as-prepared materials were characterized by XRD, TEM, PL spectra, and magnetic measurement respectively. The nanorods are 80-250 nm in diameter and about 3 μm in length. X-ray diffraction data, TEM images confirm that the materials synthesized in optimal conditions are ZnO:Co single crystalline solid solution without any impurities related to Co. The PL spectra show that the ferromagnetic samples exhibit strong Zn interstitials and oxygen vacancy emission indicating defects may stabilize ferromagnetic order in the obtained diluted magnetic semiconductors. Magnetic measurements show that the Zn(1-x)Co(x)O nanorods exist obvious ferromagnetic characteristics with T(c) above 300 K. M(s) and coercivities first increase and then decrease with dopant concentration increasing, reaching the highest for 3% doping level. The structural and magnetic properties of these samples support the hypothesis that the FM of DMS nanorods is due to a defect mediated mechanism instead of cobalt nanoclusters and carrier mediated.

Yttrium-doped ZnO (YZO) nanorods were synthesized by hydrothermal growth on a quartz substrate with various post-annealing temperatures. To investigate the effects of post-annealing on the optical properties and parameters of the nanorods, X-ray diffractometry (XRD), photoluminescence (PL) measurement, and ultraviolet (UV)-visible spectroscopy were used. From the XRD investigation, the full width at half maximum (FWHM) and the dislocation density of the nanorods was found to increase with an increase in the post-annealing temperature. In the PL spectra, the intensity of the near band edge (NBE) emission peak in the UV region also increases with an increase in the temperature of post-annealing. The deep level emission (DLE) peak in the visible region changes with various post-annealing temperatures, and its intensity increases remarkably with post-annealing at 800 degrees C. In this paper, changes in the optical parameters of the nanorods caused by variation in the behavior of Y during post-annealing was investigated, with properties such as absorption coefficients, refractive indices, and dispersion parameters being obtained from transmittance and reflectance analysis.

In this study, undoped and yttrium (Y) doped nanocrystalline hydroxyapatite crystals were synthesized by the hydrothermal method at 180 Degree-Sign C for 24 h. Highly ordered and oriented hydroxyapatite (HAp) nanorods were prepared by yttrium doping and their nanostructure and physical properties were compared with those of undoped HAp rods. FESEM images showed that the doping with Y ions reduced the diameter (from 25 nm to 15 nm) and increased the length (from 95 nm to 115 nm) of the synthesized rods. The aspect ratio of the undoped and Y-dopednanorods were calculated to be 4.303 (SD = 0.0959) and 7.61 (SD = 0.0355), respectively. Specific surface area (SSA) analysis showed that SSA also increased from 66.74 m{sup 2}/g to 68.57 m{sup 2}/g with the addition of yttrium. Y-doped HAp nanorod reinforced HMWPE composites displayed the better mechanical performance than those reinforced with pure HAp nanorods. The possible strengthening of nanorods and the increase of SSA due to the reduction in the size of nanorods in the presence of yttrium may have contributed to the strengthening of Y-doped HAp/HMWPE composites. - Graphical Abstract: Highly ordered and oriented yttrium doped hydroxyapatite (HAp) nanorods were prepared by hydrothermal method. For undoped HAp the average length of the nanorod is 95 nm with mean diameter of 24 nm and for a Y dopednanorod the average length is {approx} 115 nm and the mean diameter is 15 nm. Mechanical analysis was carried out by polymer/nanoparticle composite method. Highlights: Black-Right-Pointing-Pointer Yttrium doped hydroxyapatite nanorods were prepared by hydrothermal method. Black-Right-Pointing-Pointer The nanorods have highly uniform size distribution. Black-Right-Pointing-Pointer Yttrium substitution and nanostructure formation was confirmed by careful analysis. Black-Right-Pointing-Pointer Mechanical strength was analyzed by polymer nanoparticle reinforcement method.

Solar energy utilization is an attractive option for new energy technology and economic development. Our research is the formulation of catalyst materials for solar production of hydrogen from water. Titanium(IV) oxide has been explored for water splitting; however, a major challenge is that titanium(IV) oxide can only absorb UV light. Visible light absorption can be increased by metal ion or anion doping by creating interband states. Most dopant protocols lead to deposition of dopant ions throughout the solid, and interfacial deposition has received very little attention. We have developed a method to selectively attach transition metal ions and lanthanide ions on the surface of titanium(IV) oxide nanorods using metal chlorides as precursors. The present study demonstrates that Cr(III), Mn(II), Fe(II), Co(II), Ni(II), Cu (II), Eu(III), Ce(III), Pr(III) and Er(III) were coordinated to the surface of oleic acid capped TiO2 nanorods (NRs) by post-synthesis method without any phase or morphology transformation. Metal ion loading could be carefully controlled, and we show a titration curve for addition of transition metal ions and Eu(III) to the nanorod surface. The materials were characterized with UV-visible spectroscopy, transmission electron microscopy, elemental analysis, XPS and powder X-ray diffraction. X-ray photoelectron spectra were obtained for a series of M-TiO2 samples in which transition metal (M = Cr, Mn, Fe, Co, Ni, Cu) ions are directly attached to the surface of anatase TiO2 nanocrystals. Further, we report sequential, quantitative loading of transition metal ions (Cr, Mn, Fe, Co, Ni, Cu) to the surface of rod-shape anatase TiO2 nanocrystals in bimetallic combinations (6C2 = 15). TEM, PXRD, UV-Vis, XPS and elemental analysis characterization show that bimetallic combinations were synthesized successfully.

Solution synthesis of nanorods is currently an important area of study due to the precision required to engender advantages in a wide range of fields. Viruses provide a template for synthesis in order to form uniform metalnanorods at mild operating conditions, without the use of expensive technology. In recent years, many materials involving the Tobacco mosaic virus (TMV) and its variants have been synthesized in attempts to produce high quality nanomaterials. However, the underlying processes involved in virion mineralization have not been sufficiently studied to allow for directed synthesis. The fundamental study of the hydrothermal synthesis of palladium on biotemplates, which produces uniform, controllable, monodisperse palladium nanorods, is of interest in this thesis. Three different experimental studies are outlined in this thesis. In situ X-ray absorption spectroscopy (XAS) was employed in order to characterize the reduction and growth mechanisms of palladium (Pd) on the surface of genetically engineered TMV. XAS, via XANES and EXAFS analysis was combined with TEM to confirm an autocatalytic reduction, mediated by the TMV1Cys surface. This reduction interestingly proceeds via two first order regimes, which result in two linear growth regimes as spherical palladium nanoparticles are formed. Results in this project served as an entryway into fundamentally understanding virus-mediated reduction and the relationship between the underlying reduction and growth processes governing mineralization. Pd biomineralization was further elucidated by reframing it within commonly known molecular processes. These included the individual adsorption, reduction, and nanocrystal growth processes, which simultaneously occur during the hydrothermal synthesis on TMV. The adsorption of precursor and reduction of palladium were decoupled through UV-Vis Spectroscopy and in situ XAS studies. The role of additional cysteine (Cys) residues, ionic strength, and coating density on the

Al doped ZnO nanorods (NR's) having Al concentration up to 10 mol% were grown by the hydrothermal method. XRD measurements showed that the Al substituted ZnO NR's maintained the hexagonal wurtzite structure for all levels of Al substitution. EDX measurements of the ZnO:Al NR's indicated that the Al substitution created additional Zn vacancies in the wurtzite structure which is reflected in the enhanced photoluminescence emission in the visible light spectra between 450 and 550 nm of the more heavily doped ZnO:Al NR's. SEM images of the heavier doped ZnO:Al nanorods showed nano nodules being formed on the surface of the hexagonal shaped NR's. The saturation magnetizations of the ZnO:Al NR's as measured by a SQUID magnetometer increased to 10.66×10-4 emu/g as more Al was substituted in. The hysteresis loops for the ZnO:Al NR's began to exhibit novel effects, such as horizontal shift (exchange bias field 0.0382 kOe for the 9 mol% NR) and butterfly shapes.

Eu/Tb co-doped ZnO nanorods were prepared by co-precipitation method and the effect of Eu-Tb co-doping was studied by X-ray diffraction (XRD), transmission electron microscopy (TEM), high resolution transmission electron microscopy, Fourier transform infrared spectroscopy (FTIR), UV-Vis-NIR diffuse reflectance (DR) and photoluminescence (PL) spectroscopy. The XRD pattern shows typical peak pattern for pure hexagonal wurtzite structure to match with the JCPDS data. The samples are found to be consisting of nanorods of diameter 20-30 nm as revealed by the TEM image. The FTIR pattern confirms the formation of the compounds. The DR study was carried to show the variation of absorption edge and the variation in band gap values, which showed the crystal size effect in the co-doped sample of different rare-earth ratios. The room temperature PL study shows bright emission spectra for the samples with different rare-earth ratios. It shows a very good energy transfer from Tb to Eu ions. The energy transfer mechanism and color tunability were discussed thoroughly.

Highlights: • TiO{sub 2} nanorodsdoped with Ca ions were synthesized by one-step hydrothermal method. • The flat band edge of rutile TiO{sub 2} shifted positively via Ca-doping. • The photoelectric conversion efficiency of dye-sensitized solar cells (DSSCs) based on TiO{sub 2} electrode was much enhanced by Ca-doping. • A relatively high open circuit voltage was obtained by adopting Ca-doped TiO{sub 2} nanorods electrode. - Abstract: Ca-doped TiO{sub 2} nanorod arrays were prepared via the one-step hydrothermal method successfully, and the effect of Ca ions content on the photovoltaic conversion efficiency of dye-sensitized solar cells has been fully discussed in the paper. Although no obvious change on the microstructure and morphology was observed by field emission scanning electron microscope and transmission electron microscope for the Ca-doped samples, the results of X-ray diffraction and X-ray photoelectron spectroscopy confirmed that Ti{sup 4+} was substituted with Ca{sup 2+} successfully. UV–vis spectroscopy results revealed that the flat band edge shifted positively by Ca ions doping. The photovoltaic conversion efficiency of the dye-sensitized solar cells based on the 2 mol% Ca-doped TiO{sub 2} electrode was 43% higher than that of the undoped one due to the less recombination possibility.

Titanium dioxide (TiO2) nanorods with nanocavities doped with chromium (Cr) were synthesized by hydrothermal method. The morphology of prepared nanorods was determined by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy dispersive X-ray spectroscopy (EDX). The electrorheological (ER) behaviour of suspensions based on TiO2 was investigated under the steady shear, and the yield stress was chosen as a suitable tool for a comparison of ER performance. Some optimum in level of Cr doping of TiO2 was found.

Two methods have been considered for the deposition of silver nanorods onto conventional glass substrates. In the first method, silver nanorods were deposited onto 3-(aminopropyl)triethoxysilane-coated glass substrates simply by immersing the substrates into the silver nanorod solution. In the second method, spherical silver seeds that were chemically attached to the surface were subsequently converted and grown into silver nanorods in the presence of a cationic surfactant and silver ions. The size of the silver nanorods was controlled by sequential immersion of silver seed-coated glass substrates into a growth solution and by the duration of immersion, ranging from tens of nanometers to a few micrometers. Atomic force microscopy and optical density measurements were used to characterize the silver nanorods deposited onto the surface of the glass substrates. The application of these new surfaces is for metal-enhanced fluorescence (MEF), whereby the close proximity of silver nanostructures can alter the radiative decay rate of fluorophores, producing enhanced signal intensities and an increased fluorophore photostability. In this paper, it is indeed shown that irregularly shaped silver nanorod-coated surfaces are much better MEF surfaces as compared to traditional silver island or colloid films. Subsequently, these new silver nanorod preparation procedures are likely to find a common place in MEF, as they are a quicker and much cheaper alternative as compared to surfaces fabricated by traditional nanolithographic techniques.

One-dimensional pure zinc oxide (ZnO) and Y-doped ZnO nanorod arrays have been successfully fabricated on the silicon substrate for comparison by a simple hydrothermal process at the low temperature of 90°C. The Y-dopednanorods exhibit the same c-axis-oriented wurtzite hexagonal structure as pure ZnO nanorods. Based on the results of photoluminescence, an enhancement of defect-induced green-yellow visible emission is observed for the Y-doped ZnO nanorods. The decrease of E2(H) mode intensity and increase of E1(LO) mode intensity examined by the Raman spectrum also indicate the increase of defects for the Y-doped ZnO nanorods. As compared to pure ZnO nanorods, Y-doped ZnO nanorods show a remarked increase of saturation magnetization. The combination of visible photoluminescence and ferromagnetism measurement results indicates the increase of oxygen defects due to the Y doping which plays a crucial role in the optical and magnetic performances of the ZnO nanorods.

Doped and undoped ZnO nanorod arrays were produced combining atomic layer deposition and hydrothermal processes. First, a ZnO layer with preferential orientation normal to the c-axis was grown on the substrate by means of the decomposition of diethylzinc; subsequently, the nanorod arrays were produced through solvothermal process using a solution of Zn(NO3)2 as precursor. Doped ZnO nanorods were produced using Ce(C2H3O2)3·H2O as dopant agent precursor. Undoped and Ce-doped ZnO nanorod arrays showed high-intensity photoluminescence. The doping concentration of x = 0.04 (Zn1- x Ce x O) displayed the highest photoluminescence. Undoped ZnO showed an intense UV peak centered at 382 nm with a narrow full wide half maximum of 33 nm. Ce-doped ZnO PL spectra contain three bands, one signal in the UV region centered at 382 nm, other centered at 467 nm in the near-green region and other one emission centered at 560 nm. The results herein exposed demonstrate the capability to produce high-quality ZnO and Zn1- x Ce x O films.

Zinc oxide (ZnO) is a n-type semiconductor material which has a wide direct band gap energy of ∼ 3.3 eV, and other interesting optical properties, hence it’s potentially applied to various fields such as electronics, optoelectronics, sensors, photonic devices, and also photocatalyst. Dopant in ZnO nanostructures is an effective way to improve ZnO’s structural properties in various applications. In this study, undoped and Ce doped ZnO nanorods were synthesized on ITO coated glass substrates by ultrasonic spray pyrolysis for seeding deposition and hydrothermal methods at a temperature of 95 0C for 2 hours for growth. X-ray diffraction, field emission scanning electron microscopy (FESEM), UV-VIS and Photoluminescence spectroscopy were used to characterize the crystal structure, surface morphology and optical properties of ZnO nanorods and the photocatalytic activity test for methylene blue degradation. The experimental results showed that 3% Cerium dopant has produced hexagonal morphology ZnO nanorod growing more uniform on (002) crystal planes, increased the intensity of ultraviolet absorbance thereby increase the degradation speed of methylene blue.

The incorporation of foreign elements into ZnO nanostructures is of significant interest for tuning the structure and optical and electrical properties in nanoscale optoelectronic devices. In this study, Ga-doped 1-D ZnO nanorods were synthesized using a hydrothermal route, in which the doping content of Ga was varied from 0% to 10%. The pn heterojunction diodes based on the n-type Ga-doped ZnO nanorod/p-type Si substrates were constructed, and the effect of the Ga doping on the morphology, chemical bonding structure, and optical properties of the ZnO nanorods was systematically investigated as well as the diode performance. With increasing Ga content, the average diameter of the ZnO nanorods was increased, whereas the amount of oxygen vacancies was reduced. In addition, the Ga-doped ZnO nanorod/p-Si diodes showed a well-defined rectifying behavior in the I-V characteristics and an improvement in the electrical conductivity (diode performance) by the Ga doping, which was attributed to the increased charge carrier (electron) concentration and the reduced defect states in the nanorods by incorporating Ga. The results suggest that Ga doping is an effective way to tailor the morphology, optical, electronic, and electrical properties of ZnO nanorods for various applications such as field-effect transistors (FETs), light-emitting diodes (LEDs), and laser diodes (LDs).

Cobalt-doped Gd2O3 (Gd2-xCoxO3, 0≤x≤0.06) nanorods of about 100 nm diameter and 2 μm length were synthesized using a simple hydrothermal method. XRD, Raman, XPS, and TEM measurements showed the samples to have a single cubic phase structure of Gd2O3 doped with Co2+ cations, without any cobalt clusters. All the samples showed paramagnetism at room temperature as well as at 5 K. The samples' high magnetization values at 5 K were due to reduction of the thermal randomization of the magnetic spins. The Curie-Weiss fitting of the magnetic data reflected antiferromagnetism along with paramagnetism due to the exchange interactions of Gd3+ via O2- ions and coupling between Co2+-Co2+ pairs.

In this paper, a two-step process is developed to synthesize rare earth doped titania nanorods (RE–TiO2 NRs) as photocatalysts for efficient degradation of lignin under simulated sunlight irradiation. In this approach, protonated titanate nanotubes with layered structures were first prepared by a hydrothermal approach, and rare earth metal ions were subsequently bound to the negatively charged surface of the synthesized titanate via electrostatic incorporation. The as-synthesized RE–TiO2 NRs after calcination generally showed much higher photocatalytic efficiencies than those of undoped TiO2 NRs or the commercial P25 TiO2 photocatalyst. Using methyl orange (MO) as a probing molecule, we demonstrate that Eu–TiO2 NRs are among the best for degrading MO, with an observed rate constant of 4.2 × 10-3 s-1. The La3+, Sm3+, Eu3+ and Er3+doped TiO2 NRs also showed higher photocatalytic efficiencies in degrading MO than the commercial P25 TiO2. Finally, we further demonstrate that lignin can be photodegraded effectively and rapidly at room temperature under simulated sunlight through two reaction routes, which could be important in controlling ways of lignin depolymerization or the formation of reaction products.

Up-conversion luminescence in rare earth ions (REs) doped nanoparticles has attracted considerable research attention for the promising applications in solid-state lasers, three-dimensional displays, solar cells, biological imaging, and so forth. However, there have been no reports on REs doped nanoparticles to investigate their polarized energy transfer up-conversion, especially for single particle. Herein, the polarized energy transfer up-conversion from REs doped fluoride nanorods is demonstrated in a single particle spectroscopy mode for the first time. Unique luminescent phenomena, for example, sharp energy level split and singlet-to-triplet transitions at room temperature, multiple discrete luminescence intensity periodic variation with polarization direction, are observed upon excitation with 980 nm linearly polarized laser. Furthermore, nanorods with the controllable aspect ratio and symmetry are fabricated for analysis of the mechanism of polarization anisotropy. The comparative experiments suggest that intraions transition properties and crystal local symmetry dominate the polarization anisotropy, which is also confirmed by density functional theory calculations. Taking advantage of the REs based up-conversion, potential application in polarized microscopic multi-information transportation is suggested for the polarization anisotropy from REs doped fluoride single nanorod or nanorod array.

Summary Ce-doped ZnO (ZnO:Ce) nanorods have been prepared through a solvothermal method and the effects of Ce-doping on the structural, optical and electronic properties of ZnO rods were studied. ZnO:Ce rods were characterized by XRD, SEM, TEM, XPS, BET, DRS and Raman spectroscopy. 5% Ce-doped ZnO rods with an average length of 130 nm and a diameter of 23 nm exhibit the highest photocatalytic activity for the degradation of the Orange II dye under solar light irradiation. The high photocatalytic activity is ascribed to the substantially enhanced light absorption in the visible region, to the high surface area of ZnO:Ce rods and to the effective electron–hole pair separation originating from Ce doping. The influence of various experimental parameters like the pH, the presence of salts and of organic compounds was investigated and no marked detrimental effect on the photocatalytic activity was observed. Finally, recyclability experiments demonstrate that ZnO:Ce rods are a stable solar-light photocatalyst. PMID:27826508

Ce-doped ZnO (ZnO:Ce) nanorods have been prepared through a solvothermal method and the effects of Ce-doping on the structural, optical and electronic properties of ZnO rods were studied. ZnO:Ce rods were characterized by XRD, SEM, TEM, XPS, BET, DRS and Raman spectroscopy. 5% Ce-doped ZnO rods with an average length of 130 nm and a diameter of 23 nm exhibit the highest photocatalytic activity for the degradation of the Orange II dye under solar light irradiation. The high photocatalytic activity is ascribed to the substantially enhanced light absorption in the visible region, to the high surface area of ZnO:Ce rods and to the effective electron-hole pair separation originating from Ce doping. The influence of various experimental parameters like the pH, the presence of salts and of organic compounds was investigated and no marked detrimental effect on the photocatalytic activity was observed. Finally, recyclability experiments demonstrate that ZnO:Ce rods are a stable solar-light photocatalyst.

Calcium sulfate (CaSO4) doped with proper activators is a highly sensitive phosphor used in different fields mainly for radiation dosimetry, lighting and display applications. In this work pure and dopednanorods of CaSO4 were produced by the co-precipitation technique. Samples from this material doped with Ag, Cu, Dy, Eu and Tb were exposed to different doses of 15 MeV e-beam and studied for their thermoluminesence (TL) and photoluminescence (PL) properties. Color center formation leading to PL emissions were investigated before and after e-beam irradiation. The samples doped with rare earths elements (i.e. Dy, Eu and Tb) were observed to have thinner nanorods than the other samples and have higher absorption in the UV region. The Ag and Tb doped samples have poor TL response to e-beam, while those activated by Cu, Dy and Eu have strong glow peaks at around 123 °C. Quite linear response curves in the whole studied exposures i.e. 0.1-100 Gy were also observed in Cu and Dy doped samples. The PL results show that pure CaSO4 nanorods have active color centers without irradiation, which could be enriched/modified by these impurities mainly rare earths and further enhanced by e-beam irradiation. Eu3+ → Eu2+ conversion is clearly observed in Eu doped sample after e-beam irradiation. These results show that these nanorods might be useful in lighting and display devices development.

A catalytically active oxide support in combination with metal catalysts is required in order to achieve better low temperature activity and selectivity. Here, we report that CeO2 nanorods with a superior surface oxygen release/storage capability were used as an active support of transition metal (TM) catalysts (Mn, Fe, Co, Ni, Cu) for CO oxidation reaction. The as-prepared CeO2 nanorods supported 10 wt% TM catalysts were highly active for CO oxidation at low temperature, except for the Fe sample. It is found that the 10%Cu-CeO2 catalyst performed best, and it provided a lower light-off temperature with T50 (50% conversion) at 75 °C and T100 (100% conversion) of CO to CO2 at 194 °C. The atomic level surface structure of CeO2 nanorods was investigated in order to understand the improved low temperature catalytic activity. The richness of surface roughness and various defects (voids, lattice distortion, bending, steps, twinning) on CeO2 nanorods could facilitate oxygen release and storage. According to XRD and Raman analysis, copper species migrate into the bulk CeO2 nanorods to a greater degree. Since CO adsorbed over the surface of the catalyst/support is detrimental to its catalytic activity, the surface defects on the CeO2 nanorods and CeO2-TM interactions were critical to the enhanced activity.

In this paper, N-doped TiO2 (N-TiO2) nanorod arrays were synthesized with hydrothermal method, and perovskite solar cells were fabricated using them as electron transfer layer. The solar cell performance was optimized by changing the N doping contents. The power conversion efficiency of solar cells based on N-TiO2 with the N doping content of 1% (N/Ti, atomic ratio) has been achieved 11.1%, which was 14.7% higher than that of solar cells based on un-doped TiO2. To get an insight into the improvement, some investigations were performed. The structure was examined with X-ray powder diffraction (XRD), and morphology was examined by scanning electron microscopy (SEM). Energy dispersive spectrometer (EDS) and Tauc plot spectra indicated the incorporation of N in TiO2 nanorods. Absorption spectra showed higher absorption of visible light for N-TiO2 than un-doped TiO2. The N doping reduced the energy band gap from 3.03 to 2.74 eV. The photoluminescence (PL) and time-resolved photoluminescence (TRPL) spectra displayed the faster electron transfer from perovskite layer to N-TiO2 than to un-doped TiO2. Electrochemical impedance spectroscopy (EIS) showed the smaller resistance of device based on N-TiO2 than that on un-doped TiO2.

In this paper, N-doped TiO2 (N-TiO2) nanorod arrays were synthesized with hydrothermal method, and perovskite solar cells were fabricated using them as electron transfer layer. The solar cell performance was optimized by changing the N doping contents. The power conversion efficiency of solar cells based on N-TiO2 with the N doping content of 1% (N/Ti, atomic ratio) has been achieved 11.1%, which was 14.7% higher than that of solar cells based on un-doped TiO2. To get an insight into the improvement, some investigations were performed. The structure was examined with X-ray powder diffraction (XRD), and morphology was examined by scanning electron microscopy (SEM). Energy dispersive spectrometer (EDS) and Tauc plot spectra indicated the incorporation of N in TiO2 nanorods. Absorption spectra showed higher absorption of visible light for N-TiO2 than un-doped TiO2. The N doping reduced the energy band gap from 3.03 to 2.74 eV. The photoluminescence (PL) and time-resolved photoluminescence (TRPL) spectra displayed the faster electron transfer from perovskite layer to N-TiO2 than to un-doped TiO2. Electrochemical impedance spectroscopy (EIS) showed the smaller resistance of device based on N-TiO2 than that on un-doped TiO2.

Exerting control over the near-infrared (NIR) plasmonic response of nanosized metals and semiconductors can facilitate access to unexplored phenomena and applications. Here we combine electrostatic self-assembly and Cd(2+)/Cu(+) cation exchange to obtain an anisotropic core-shell nanoparticle cluster (NPC) whose optical properties stem from two dissimilar plasmonic materials: a gold nanorod (AuNR) core and a copper selenide (Cu(2-x)Se, x ≥ 0) supraparticle shell. The spectral response of the AuNR@Cu2Se NPCs is governed by the transverse and longitudinal plasmon bands (LPB) of the anisotropic metallic core, since the Cu2Se shell is nonplasmonic. Under aerobic conditions the shell undergoes vacancy doping (x > 0), leading to the plasmon-rich NIR spectrum of the AuNR@Cu(2-x)Se NPCs. For low vacancy doping levels the NIR optical properties of the dually plasmonic NPCs are determined by the LPBs of the semiconductor shell (along its major longitudinal axis) and of the metal core. Conversely, for high vacancy doping levels their NIR optical response is dominated by the two most intense plasmon modes from the shell: the transverse (along the shortest transversal axis) and longitudinal (along the major longitudinal axis) modes. The optical properties of the NPCs can be reversibly switched back to a purely metallic plasmonic character upon reversible conversion of AuNR@Cu(2-x)Se into AuNR@Cu2Se. Such well-defined nanosized colloidal assemblies feature the unique ability of holding an all-metallic, a metallic/semiconductor, or an all-semiconductor plasmonic response in the NIR. Therefore, they can serve as an ideal platform to evaluate the crosstalk between plasmonic metals and plasmonic semiconductors at the nanoscale. Furthermore, their versatility to display plasmon modes in the first, second, or both NIR windows is particularly advantageous for bioapplications, especially considering their strong absorbing and near-field enhancing properties.

Ti-doped ZnO nanorod arrays were grown onto Si substrate using chemical bath deposition (CBD) method at 93 °C. To investigate the effect of time deposition on the morphological, and structural properties, four Ti-doped ZnO samples were prepared at various deposition periods of time (2, 3.5, 5, and 6.5 h). FESEM images displayed high-quality and uniform nanorods with a mean length strongly dependent upon deposition time; i.e. it increases for prolonged growth time. Additionally, EFTEM images reveal a strong erosion on the lateral side for the sample prepared for 6.5 h as compared to 5 h. This might be attributed to the dissolution reaction of ZnO with for prolonged growth time. XRD analysis confirms the formation of a hexagonal wurtzite-type structure for all samples with a preferred growth orientation along the c-axis direction. The (100) peak intensity was enhanced and then quenched, which might be the result of an erosion on the lateral side of nanorods as seen in EFTEM. This study confirms the important role of growth time on the morphological features of Ti-doped ZnO nanorods prepared using CBD.

ZnO seed layers were deposited onto a quartz substrate using the sol--gel method, and Al-doped ZnO (AZO) nanorod array thin films with different Al concentrations that ranged from 0 to 2.0 at. % were grown on the ZnO seed layers via the hydrothermal method. Optical parameters, including the optical band gap, the absorption coefficient, the Urbach energy, the refractive index, the dispersion parameter, and the optical conductivity, were studied to investigate the effects of Al doping on the optical properties of AZO nanorod array thin films. The optical band gaps of the ZnO and AZO nanorod array thin films were 3.206 at 0 at.%, 3.214 at 0.5 at.%, 3.226 at 1.5 at.%, and 3.268 at 2.0 at.%. The Urbach energy gradually decreased from 126 meV (0 at.%) to 70 meV (2.0 at.%) as the Al concentration was increased. The dispersion energy, the single-oscillator energy, the average oscillator wavelength, the average oscillator strength, the refractive index, and the optical conductivity of the AZO nanorod array thin films were all affected by Al doping.

Ti-doped ZnO nanorod arrays were grown onto Si substrate using chemical bath deposition (CBD) method at 93 °C. To investigate the effect of time deposition on the morphological, and structural properties, four Ti-doped ZnO samples were prepared at various deposition periods of time (2, 3.5, 5, and 6.5 h). FESEM images displayed high-quality and uniform nanorods with a mean length strongly dependent upon deposition time; i.e. it increases for prolonged growth time. Additionally, EFTEM images reveal a strong erosion on the lateral side for the sample prepared for 6.5 h as compared to 5 h. This might be attributed to the dissolution reaction of ZnO with for prolonged growth time. XRD analysis confirms the formation of a hexagonal wurtzite-type structure for all samples with a preferred growth orientation along the c-axis direction. The (100) peak intensity was enhanced and then quenched, which might be the result of an erosion on the lateral side of nanorods as seen in EFTEM. This study confirms the important role of growth time on the morphological features of Ti-doped ZnO nanorods prepared using CBD.

Nanostructured fluorine-doped α-Fe2O3 nanorods were synthesized based on a one-step low temperature hydrothermal method. The XPS results verified that fluorine has been successfully incorporated into the hematite lattice. The delivered lithium capacity was effectively improved owing to the fluorine doping comparing with the pristine α-Fe2O3. The increase in electrochemical capacity of fluorine-doped α-Fe2O3 was then studied from the pointviews of nanostructure, electronic properties, and magnetic characteristics.

The facile and sensitive strategies for detections of nitroaromatic explosives are highly desirable in many challenging environments, especially for homeland security against terrorism. Here, we inkjet printed polyethylenimine (PEI)-coated Ce, Tb co-doped NaGdF4 nanorods (NaGdF4:Ce/Tb NRs) onto common filter paper to construct test paper for visual and instant detections of a typical explosive 2,4,6-trinitrophenol (TNP). Polyethylenimine molecules not only facilitate the formation of uniform NaGdF4 nanorods but also provide specific recognized sites for TNP by the acid-base pairing interaction. The resultant TNP bound at the surface of PEI-coated NaGdF4:Ce/Tb NRs can strongly quench the phosphorescence with a remarkably high quenching constant by the charge transfer mechanism from NaGdF4:Ce/Tb NRs to TNP. By printing of the probe on a piece of filter paper, trace amounts of TNP can be visually detected by the appearance of a dark color against a bright green background under a UV lamp. This test paper can detect TNP as low as 0.45 ng mm(-2) by the naked eye, which provides a potential application in the rapid, on-line detections of explosives.

Heavy-phosphorus-doped silicon anodes were fabricated on CuO nanorods for application in high power lithium-ion batteries. Since the conductivity of lithiated CuO is significantly better than that of CuO, after the first discharge, the voltage cut-off window was then set to the range covering only the discharge–charge range of Si. Thus, the CuO core was in situ lithiated and acts merely as the electronic conductor in the following cycles. The Si anode presented herein exhibited a capacity of 990 mAh/g at the rate of 9 A/g after 100 cycles. The anode also presented a stable rate performance even at a current density as high as 20 A/g. PMID:28243560

Immobilized photocatalysts with high catalytic activity under UV light were prepared by growing Cr-doped ZnO nanorods on glass substrates by a hydrothermal method. The effects of Cr dopant on the surface texture, crystallinity, surface chemistry, and photoinduced charge separation and their relation with the photocatalytic degradation of Cr-doped ZnO were investigated by scanning electron microscopy, diffuse reflectance spectra, photoelectrochemical scanning electrochemical microscopy, and X-ray photoemission spectroscopy. Adding the appropriate amount of Cr dopant is a powerful way to enhance the separation of charge carriers in ZnO photocatalyst. The photocatalytic activity was improved due to the increase in surface oxygen vacancies, the separation of charge carriers, modification of the band gap, and the large surface area of the doped ZnO nanorod photocatalyst. - Graphical abstract: Photoinduced charge separation and its relation with the photocatalytic degradation activity of Cr-doped ZnO were investigated by photoelectrochemical scanning electrochemical microscopy. - Highlights: • Cr dopant enhances separation of charge carries in ZnO nanorod photocatalyst. • Photoinduced charge carries separation monitored by PEC-SECM. • The higher the photocurrent is, the higher the photocatalytic activity is. • Degradation of DB86 dye solutions under visible light finished within 50 min. • Higher activity due to more oxygen vacancy, tuned band gap and more surface area.

In this study we present results on electrochemically grown ZnO nanorods on different metal oxide underlays, such as ZnO seed layers with different morphologies, ZnS and TiO2 compact thin films produced by spray pyrolysis on transparent conductive oxide (TCO) substrates. Also in this work we present results on ZnO nanorods directly deposited on some chosen TCO substrates. The relationship between nanorod formation and substrate properties were studied. All ZnO nanorod layers were grown electrochemically using ZnCl2 aqueous solutions (c=0.2 mmol/L) at the bath temperature of 80 °C during one hour. The structural properties and morphology of metal oxide underlays and ZnO nanorods grown on them were studied by scanning electron microscopy (SEM), x-ray diffraction spectroscopy (XRD). Depending on the substrate morphology, ZnO rods with different dimension, orientation, shape and density were obtained. For instance, larger rods (d~200 nm, l~700 nm) were obtained on substrates, such as ITO/glass, FTO/glass and ZnO:In/ITO/glass. Smaller rods (d~60 nm, l~350 nm) were obtained on smooth, uniform and fine-grained underlays, such as ZnS and TiO2.

Disclosed herein is a sol-gel polymerization process for synthesizing metal-doped organic gels. The process polymerizes metal salts of hydroxylated benzenes or hydroxylated benzene derivatives with alkyl or aryl aldehydes to form metal-doped, wet, organic gels. The gels can then be dried by supercritical solvent extraction to form metal-doped aerogels or by evaporation to form metal-doped xerogels. The aerogels and xerogels can then be pyrolyzed.

Disclosed herein is a sol-gel polymerization process for synthesizing metal-doped organic gels. The process polymerizes metal salts of hydroxylated benzenes or hydroxylated benzene derivatives with alkyl or aryl aldehydes to form metal-doped, wet, organic gels. The gels can then be dried by supercritical solvent extraction to form metal-doped aerogels or by evaporation to form metal-doped xerogels. The aerogels and xerogels can then be pyrolyzed.

Fe doped ZnO nanowires, nanorods, and urchin-like nanostructures have been grown using an evaporation-deposition method with compacted mixtures of ZnS and Fe2O3 powders, with different Fe contents as precursors. Treatments at 950 °C under argon flow lead to the growth of iron doped nanowires, nanorods, and other nanostructures on the surface of the compacted sample. The incorporation of iron into the nanostructures has been investigated via energy dispersive spectroscopy as well as by cathodoluminescence in a scanning electron microscope and photoluminescence in an optical microscope. The iron content in the structures is limited to the range of 0.5-0.7 at.% and does not depend on the content in the precursor. Bright and dark field imaging and twist contour analysis via transmission electron microscopy support the possibility of a dislocation driven growth of the nanowires.

We report the first demonstration of cobalt phosphate (Co-Pi)-assisted molybdenum-doped zinc oxide nanorods (Zn(1-x)Mo(x)O NRs) as visible-light-sensitive photofunctional electrodes to fundamentally improve the performance of ZnO NRs for photoelectrochemical (PEC) water splitting. A maximum photoconversion efficiency as high as 1.05% was achieved, at a photocurrent density of 1.4 mA cm(-2). More importantly, in addition to achieve the maximum incident photon to current conversion efficiency (IPCE) value of 86%, it could be noted that the IPCE of Zn(1-x)Mo(x)O photoanodes under monochromatic illumination (450 nm) is up to 12%. Our PEC performances are comparable to those of many oxide-based photoanodes in recent reports. The improvement in photoactivity of PEC water splitting may be attributed to the enhanced visible-light absorption, increased charge-carrier densities, and improved interfacial charge-transfer kinetics due to the combined effect of molybdenum incorporation and Co-Pi modification, contributing to photocatalysis. The new design of constructing highly photoactive Co-Pi-assisted Zn(1-x)Mo(x)O photoanodes enriches knowledge on doping and advances the development of high-efficiency photoelectrodes in the solar-hydrogen field.

Charge transport across metal-semiconductor interfaces at the nanoscale is a crucial issue in nanoelectronics. Chains of semiconductor nanorods linked by Au particles represent an ideal model system in this respect, because the metal-semiconductor interface is an intrinsic feature of the nanosystem and does not manifest solely as the contact to the macroscopic external electrodes. Here we investigate charge transport mechanisms in all-inorganic hybrid metal-semiconductor networks fabricated via self-assembly in solution, in which CdSe nanorods were linked to each other by Au nanoparticles. Thermal annealing of our devices changed the morphology of the networks and resulted in the removal of small Au domains that were present on the lateral nanorod facets, and in ripening of the Au nanoparticles in the nanorod junctions with more homogeneous metal-semiconductor interfaces. In such thermally annealed devices the voltage dependence of the current at room temperature can be well described by a Schottky barrier lowering at a metal semiconductor contact under reverse bias, if the spherical shape of the gold nanoparticles is considered. In this case the natural logarithm of the current does not follow the square-root dependence of the voltage as in the bulk, but that of V(2/3). From our fitting with this model we extract the effective permittivity that agrees well with theoretical predictions for the permittivity near the surface of CdSe nanorods. Furthermore, the annealing improved the network conductance at cryogenic temperatures, which could be related to the reduction of the number of trap states.

Doping transition metal ions Mn2+ to semiconductor quantum dots (QDs) are extremely interesting for the development of photovoltaic devices. Quantum dot sensitized solar cells (QDSCs) are able to show promising power conversion efficiencies (PCE) by employing Mn2+ doped QDs. Herein we achieve effective CdS/Mnsbnd CdSe/ZnS QDs co-sensitized vertical ZnO nanorod arrays film that provides an appreciable enhancement in photovoltaic performance. The measured PCE of the solar cells with Mn2+ doped CdSe QDs is 4.14%, which is higher than the efficiency of 2.91% for the solar cells without Mn2+ or a ∼42% increase. The improvement in PCE is ascribed to a higher open-circuit voltage (Voc = 0.74 V) and a superior short-circuit current density (Jsc = 12.6 mA cm-2) with the introduction of Mn2+ into CdSe QDs. The enhancement seen with Mn2+ doped CdSe QDs are investigated and explained by the fact that the enhanced light absorption and reduced charge recombination by the formation of Mnsbnd CdSe passivation layer covering the QDs.

The photocatalytic degradation of organophosphorus pesticide such as diazinon was investigated by Cu-doped ZnO nanorods. Cu-doped ZnO nanorods were synthesized via a facile co-precipitation method. The catalyst was characterized by XRD, FESEM, EDX, VSM, XPS, and pHzpc techniques. The effects of some operational parameters such as solution pH, Cu-doped ZnO nanorods dosage, initial diazinon concentration, oxygen and nitrogen gases, H2O2 concentration, and type of organic compounds on the degradation efficiency were discussed through the photocatalytic experiments using the Cu-doped ZnO nanorods. Neutral pH was selected as an optimal pH condition due to a photo-corrosion of ZnO in acidic and basic conditions. As the Cu-doped ZnO nanorods dosage increased up to 0.2 g/L, degradation efficiency of diazinon was continuously enhanced. Pseudo-first-order rate constant (kobs) was decreased from 0.051 to 0.0052 min(-1) and electrical energy per order (EEo) was increased from 94.12 to 923.08 (kWh/m(3)) by increasing diazinon concentration from 10 to 50 mg/L, respectively. The efficiency of the UV/Cu-doped ZnO for diazinon removal was approximately 96.97%, which was more effective than the UV/ZnO process (58.52%). Photocatalytic activity was maintained even after five successive cycles.

Ce-doped α-FeOOH nanorods with high yields were conveniently prepared by a hydrothermal method followed by an acid-treatment process. It is found that Ce uniformly distributes in the α-FeOOH nanorod nanostructures through elemental mapping analysis. The 0.5 wt% Ce-doped α-FeOOH electrode displayed excellent cycling performance with a high discharge capacity of 830 mA h g-1 after 800 charge/discharge cycles at a high current of 2000 mA g-1. The enhanced electrochemical performance can be attributed to the improved electronic conductivity, Li-ion diffusion kinetics and structure stability after Ce doping. Furthermore, a 0.5 wt% Ce-doped α-FeOOH//LiFePO4 lithium ion cell with an initial discharge capacity of 580 mA h g-1 at 1000 mA g-1 based on the total weight of the anode material has been fabricated for the first time. The obtained 0.5 wt% Ce-doped α-FeOOH electrode as anode material for sodium-ion batteries also exhibits a high initial discharge capacity of 587 mA h g-1 at 100 mA g-1.

In this letter, we have investigated the third-order optical nonlinearities of high-quality Ni doped ZnO nanorods crystallized in wurtzite lattice, prepared by the wet chemical method. In our experiments, we found that the two photon absorption coefficient (β) increases by as much as 14 times, i.e., 7.6 ± 0.4 to 112 ± 6 cm/GW, when the Ni doping is increased from 0% to 10%. The substantial enhancement in β is discussed in terms of the bandgap scaling and Ni doping. Furthermore, we also show that the optical bandgap measured by UV-Vis and photoluminescence spectroscopies, continuously redshift with increasing Ni doping concentration. We envision that the strong nonlinear optical properties together with their dilute magnetic effects, they form an important class of materials for potential applications in magneto-optical and integrated optical chips.

In this letter, we have investigated the third-order optical nonlinearities of high-quality Ni doped ZnO nanorods crystallized in wurtzite lattice, prepared by the wet chemical method. In our experiments, we found that the two photon absorption coefficient (β) increases by as much as 14 times, i.e., 7.6 ± 0.4 to 112 ± 6 cm/GW, when the Ni doping is increased from 0% to 10%. The substantial enhancement in β is discussed in terms of the bandgap scaling and Ni doping. Furthermore, we also show that the optical bandgap measured by UV-Vis and photoluminescence spectroscopies, continuously redshift with increasing Ni doping concentration. We envision that the strong nonlinear optical properties together with their dilute magnetic effects, they form an important class of materials for potential applications in magneto-optical and integrated optical chips.

Semiconductor-metal hybrid nanostructures offer a highly controllable platform for light-induced charge separation, with direct relevance for their implementation in photocatalysis. Advances in the synthesis allow for control over the size, shape and morphology, providing tunability of the optical and electronic properties. A critical determining factor of the photocatalytic cycle is the metal domain characteristics and in particular its size, a subject that lacks deep understanding. Here, using a well-defined model system of cadmium sulfide-gold nanorods, we address the effect of the gold tip size on the photocatalytic function, including the charge transfer dynamics and hydrogen production efficiency. A combination of transient absorption, hydrogen evolution kinetics and theoretical modelling reveal a non-monotonic behaviour with size of the gold tip, leading to an optimal metal domain size for the most efficient photocatalysis. We show that this results from the size-dependent interplay of the metal domain charging, the relative band-alignments, and the resulting kinetics. PMID:26783194

The incorporation of Al, Cu co-doping in ZnO host lattice plays an important role in modification of structural, optical and electrical properties in optoelectronic devices. In the present work, we were grown one dimensional ZnO nanorods (NRs) doped with different concentration of Al (0%~5%) and Cu was kept 20 M% on ITO glass substrates using a facile hydrothermal method, and investigated the effect of the codoping on the surface morphology and the electrical and optical performances of the doped ZnO NRs as photo anodes for solar water splitting applications. The crystallite size of NRs shows tuning in the band gap between 3.194 (Zn0.79Al0.01Cu0.2O) to 3.212 eV (Zn0.75Al0.05Cu0.2O) with Aluminium doping concentration and a remarkable improvement in current density (J) from 0.05 mA/cm2 to 4.98 mA/cm2 was achieved by incorporating Al and Cu has a critical effect of ZnO nanorods.

In this work, the authors have fabricated the nanorods and nanosheets of pure and Te-doped HAp with different Te concentrations (0.04, 0.08, 0.16, 0.24wt%) by microwave-assisted technique at low temperature. The crystallite size, degree of crystallinity and lattice parameters are calculated. FE-SEM study confirms that the fabricated nanostructures are nanorods of diameter about 10nm in undoped and at low concentration of Te doping. However, at and higher concentration, it becomes nanosheets of about 5nm thickness. X-ray diffraction, FT-IR and FT-Raman studies shows that the prepared products are of HAp and Te has been successfully incorporated. From EDX the Ca/P molar ratio of the pure HAp is about 1.740, while this ratio for 0.04, 0.08, 0.16, 0.24 wt% Te doped is about 1.53, 1.678, 1.724, 1.792, respectively. Crystallite size was found to be increased with Te doping from 15nm to 62nm. The value of dielectric constant is found to be enhanced at higher concentrations of Te. The values of linear absorption coefficient were also determined and show that the prepared material with Te doping is more absorbable than pure and will be highly applicable in radiation detection applications. Furthermore, the antimicrobial potential of pure and Te doped HAp was examined against some Gram- negative and positive bacteria and fungi by agar disk diffusion method. The results demonstrated that the antimicrobial activity of Te doped HAp is stronger than that of pure HAp where it exhibited the highest activity against Bacillus subtilis>Candida albicans>Shigella dysenteriae.

Well-oriented neodymium doped SnO2 layered nanorod arrays were synthesized by a substrate-free hydrothermal route using sodium stannate and sodium hydroxide at 210 °C. The morphology and phase structure of the Nd-doped SnO2 nanoarrays were investigated by X-ray powder diffraction spectroscopy, scanning electron microscopy, transmission electron microscopy, Raman scattering spectroscopy, X-ray photoelectron spectroscopy and the BET method. The results demonstrated that the Nd-doped SnO2 layered nanorod arrays showed a unique nanostructure combined together with double layered arrays of nanorods with a diameter of 12 nm and a length of several hundred nanometers. The Nd-doped layered SnO2 nanoarrays kept the crystal structure of the bulk SnO2 and possessed more surface defects caused by the Nd ions doped into the SnO2 lattice. The Nd dopant acts as a crystallite growth inhibitor to prevent the growth of SnO2 nanorods. An investigation into the gas-sensing properties indicated that the optimized doping level of 3.0 at% Nd-doped SnO2 layered nanorod arrays exhibited an excellent sensing response toward alcohol at a lower temperature of 260 °C. The enhanced sensor performance was attributed to the higher specific surface area, multi-defect surface structure and the excellent catalytic properties of Nd dopant that is able to increase the amount of active sites on the surface of semiconducting oxides. The Nd-doped SnO2 nanoarray sensors were considered to be a promising candidate for trace alcohol detections in environmental gas monitoring.

Ga doped ZnO nanorods with homogeneous morphology grown by ultrasonic-assisted hydrothermal method on ITO substrate. The effect of hydrothermal growth times 30, 60, 90 and 120 min on the characteristics of ZnO nanorods was examined. The samples were analyzed by X-ray diffraction, scanning electron microscopy, UV-Vis spectrometer and conductivity measurement. With the optimization of the growth times (60 min), we employed Ga doped ZnO nanorods with diverse dopant concentration in fabrication of polymer solar cell. By comparing the effect of Ga doped ZnO thin films with various dopant ratio (0, 0.5, 1.0 and 2 %) on the performance of Ga doped ZnO thin films, 0.5 % Ga doped ZnO was found as the most effective doping level among the selected doping concentrations. Also using 0.5 % Ga doped ZnO thin film, Jsc of 7.54 mA/cm2, Voc of 0.541 V, and fill factor of 64.81 % were achieved, which led to power conversion efficiency of 2.64 %.

We investigate quantum nanosensors based on hybrid systems consisting of semiconductor quantum dots and metallicnanorods in the near-infrared regime. These sensors can detect biological and chemical substances based on their impact on the coherent exciton-plasmon coupling and molecular resonances supported by such systems when they interact with a laser field. We demonstrate that the ultrahigh sensitivity of such molecular resonances on environmental conditions allows dramatic and nearly instantaneous changes in the total field experienced by the semiconductor quantum dot via minuscule variations of the local refractive indices of the quantum dot or nanorod. The proposed nanosensors can utilize quantum effects to control the sense (or direction) of the changes in the quantum dot emission, allowing us to have bistable switching from dark to bright states or vice versa via adsorption (or detachment) of biomolecules. These sensors can also offer detection of ultra-small variations in the local dielectric constant of the quantum dots or metallicnanorods via coherent induction of time delays in the effective field experienced by the quantum dots when the hybrid systems interact with time-dependent laser fields. This leads to unprecedented bulk refractive index sensitivities. Our results show that one can utilize quantum phase to control the coherent exciton-plasmon dynamics in these sensors such that introduction of a biomolecule can increase or decrease the time delay. These results offer novel ways to detect single biomolecules via application of quantum coherence to convert their impact into spectacular optical events.

Molecular spins have become key enablers for exploring magnetic interactions, quantum information processes and many-body effects in metals. Metal-organic molecules, in particular, let the spin state of the core metal ion to be modified according to its organic environment, allowing localized magnetic moments to emerge as functional entities with radically different properties from its simple atomic counterparts. Here, using and preserving the integrity of transition metal phthalocyanine high-spin complexes, we demonstrate the magnetic doping of gold thin films, effectively creating a new ground state. We demonstrate it by electrical transport measurements that are sensitive to the scattering of itinerant electrons with magnetic impurities, such as Kondo effect and weak antilocalization. Our work expands in a simple and powerful way the classes of materials that can be used as magnetic dopants, opening a new channel to couple the wide range of molecular properties with spin phenomena at a functional scale.

Molecular spins have become key enablers for exploring magnetic interactions, quantum information processes and many-body effects in metals. Metal-organic molecules, in particular, let the spin state of the core metal ion to be modified according to its organic environment, allowing localized magnetic moments to emerge as functional entities with radically different properties from its simple atomic counterparts. Here, using and preserving the integrity of transition metal phthalocyanine high-spin complexes, we demonstrate the magnetic doping of gold thin films, effectively creating a new ground state. We demonstrate it by electrical transport measurements that are sensitive to the scattering of itinerant electrons with magnetic impurities, such as Kondo effect and weak antilocalization. Our work expands in a simple and powerful way the classes of materials that can be used as magnetic dopants, opening a new channel to couple the wide range of molecular properties with spin phenomena at a functional scale. PMID:27941810

Molecular spins have become key enablers for exploring magnetic interactions, quantum information processes and many-body effects in metals. Metal-organic molecules, in particular, let the spin state of the core metal ion to be modified according to its organic environment, allowing localized magnetic moments to emerge as functional entities with radically different properties from its simple atomic counterparts. Here, using and preserving the integrity of transition metal phthalocyanine high-spin complexes, we demonstrate the magnetic doping of gold thin films, effectively creating a new ground state. We demonstrate it by electrical transport measurements that are sensitive to the scattering of itinerant electrons with magnetic impurities, such as Kondo effect and weak antilocalization. Our work expands in a simple and powerful way the classes of materials that can be used as magnetic dopants, opening a new channel to couple the wide range of molecular properties with spin phenomena at a functional scale.

A novel nano-porous 3D architecture of N-doped carbon nanorods arrays grown on the surface of graphene has been prepared by carbonizing polyaniline/graphene oxide (PANI-GO) composite with PANI nanorod arrays on both sides of GO nanosheets. The obtained carbon materials are entirely composed of regularly grown carbon nanorods on graphene with height of about 100 nm and width about 30 nm, showing porous property due to the decomposition of PANI chains. The morphology of PANI grown on GO at the different growth stages was investigated to demonstrate the mechanism of the finally hierarchical architecture formation. Due to its large specific surface area and incorporation of the nitrogen groups into the carbon matrix, the obtained 3D carbon material enhances the ionic transport and the super-capacitance by synergetic effect of both double-layer and faradaic capacitances. This study provides a controllable approach to fabricate hierarchical carbon material based on conducting polymers and graphene oxide with promising applications in the high-rate electrode material of supercapacitors. PMID:25519206

Nitrogen (N)-doped titanium dioxide (TiO{sub 2}) nanorods were directly synthesized via decomposition of gas-phase titanium tetrachloride (TiCl{sub 4}) by an atmospheric microwave plasma torch. X-ray diffraction, field-emission scanning electron microscope, field-emission transmission electron microscope, and electron-energy-loss spectroscopy (EELS) have been employed to investigate fraction of the anatase and rutile phases, diameter and length, and chemical composition of the nanorods, respectively. The diameters of the nanorods are approximately 30-80 nm and the length is several micrometers. EELS data show that incorporation of N into the O site of TiO{sub 2} nanorods was enhanced in N{sub 2} gas by the microwave plasma torch. Also, a growth model of the rods was proposed on the basis of vapor-liquid-solid mechanism.

The self-assembled growth of GaN nanorods on Si (111) substrates by plasma-assisted molecular beam epitaxy under nitrogen-rich conditions is investigated. An amorphous silicon nitride layer is formed in the initial stage of growth that prevents the formation of a GaN wetting layer. The nucleation time was found to be strongly influenced by the substrate temperature and was more than 30 min for the applied growth conditions. The observed tapering and reduced length of silicon-dopednanorods is explained by enhanced nucleation on nonpolar facets and proves Ga-adatom diffusion on nanorod sidewalls as one contribution to the axial growth. The presence of Mg leads to an increased radial growth rate with a simultaneous decrease of the nanorod length and reduces the nucleation time for high Mg concentrations.

TiO2 nanorods are synthesized by a thermal corrosion. In present work, synthesis of TiO2 nanorods in anatase, rutile and Ti8O15 phases, TiO2 nanorods embedded with silver and iron oxides as dopant by using the sol-gel method and alkaline corrosion are reported. The morphologies and crystal structures of TiO2 nanorods are characterized by use of field emission scanning electron microscopy, atomic force microscopy and X-ray diffractometer techniques. The obtained results illustrate an aggregative structure at high calcined temperatures with production of spherical particles. The effects of chemical compositions and calcined temperatures on surface topography and crystallization of phases are studied. Moreover, activation energy of nanoparticles formation in pure and doped state are calculated during thermal treatment.

The biocompatibility of multifunctional nanomaterials is very important for their clinical applications. Herein, the hexagonal crystal Eu-doped GdPO4 nanorods (NRs) in the template of silk fibroin (SF) peptides are successfully synthesized via a mineralization process. The sizes of the Eu-doped GdPO4 NRs with SF peptides (SF-NRs) are ∼150 nm in length and ∼10 nm in diameter. The Eu-doped SF-NRs have strong pink luminescence and a mass magnetic susceptibility value of 1.27 emu g(-1) in 20,000 G of magnetic field due to Eu ion doping. The cell test indicates that the Eu-doped SF-NRs obviously promote the viability of cells at an NR concentration of 25-200 μg mL(-1). A growth mechanism of Eu-doped GdPO4 SF-NRs is proposed to explain their strong cellular luminescence, magnetic resonance (MR) imaging and good cyto-compatibility. Compared to NRs without SF, the Eu-doped SF-NRs not only exhibit a higher effective positive signal-enhancement ability (the longitudinal relaxivity r1 value is 1.38 (Gd mM s)(-1)) and in vivo T1 weighted MR imaging enhancement under a 7.0 T MRI system, but also show the better luminescence imaging of living cells under the fluorescence microscope. This indicates that the Eu-doped SF-NRs have potential as T1 MRI contrast agents and optical imaging probes.

Biological, physical and mechanical properties of silver-doped layers of titanium alloy Ti6Al4V and 316L steel prepared by pulsed laser deposition were studied. Metallic silver-doped coatings could be a new route for antibacterial protection in medicine. Thin films of silver and silver-doped materials were synthesized using KrF excimer laser deposition. The materials were ablated from two targets, which were composed either from titanium alloy with silver segments or from steel with silver segments. The concentration of silver ranged from 1.54 at% to 4.32 at% for steel and from 3.04 at% to 13.05 at% for titanium alloy. The layer properties such as silver content, structure, adhesion, surface wettability, and antibacterial efficacy (evaluated by Escherichia coli and Bacillus subtilis bacteria) were measured. Film adhesion was studied using scratch test. The antibacterial efficacy changed with silver doping up to 99.9 %. Our investigation was focused on minimum Ag concentration needed to reach high antibacterial efficiency, high film adhesion, and hardness.

The present study reports the synthesis of pure and Cu-doped ZnO nanorods for antibacterial and photocatalytic applications. The samples were synthesized by simple, low cost mechanical-assisted thermal decomposition process. The synthesized materials were characterized by scanning electron microscopy, UV-Visible spectroscopy, and photoluminescence studies. The antibacterial activity of characterized samples was determined against Gram-positive bacteria such as Staphylococcus aureus and Streptococcus pyogenes and Gram-negative bacteria such as Escherichia coli using shake flask method with respect to time. The significant antibacterial activity was perceived from scanning electron micrographs that clearly revealed bacterial cell lysis resulting in the release of cytoplasmic content followed by cell death. The degradation of methylene blue was used as a model organic dye for photocatalytic activity. The present study demonstrates the superior photocatalytic and antibacterial activity of Cu-doped ZnO nanorods with respect to pure ZnO nanorods.

N-doped mesoporous TiO2 nanorods were fabricated by a modified and facile sol-gel approach without any templates. Ammonium nitrate was used as a raw source of N dopants, which could produce a lot of gasses such as N2, NO2, and H2O in the process of heating samples. These gasses were proved to be vitally important to form the special mesoporous structure. The samples were characterized by the powder X-ray diffraction, X-ray photoelectron spectrometer, nitrogen adsorption isotherms, scanning electron microscopy, transmission electron microscopy, and UV-visible absorption spectra. The average length and the cross section diameter of the as-prepared samples were ca. 1.5 μm and ca. 80 nm, respectively. The photocatalytic activity was evaluated by photodegradation of methylene blue (MB) in aqueous solution. The N-doped mesoporous TiO2 nanorods showed an excellent photocatalytic activity, which may be attributed to the enlarged surface area (106.4 m2 g-1) and the narrowed band gap (2.05 eV). Besides, the rod-like photocatalyst was found to be easy to recycle.

N-doped mesoporous TiO2 nanorods were fabricated by a modified and facile sol–gel approach without any templates. Ammonium nitrate was used as a raw source of N dopants, which could produce a lot of gasses such as N2, NO2, and H2O in the process of heating samples. These gasses were proved to be vitally important to form the special mesoporous structure. The samples were characterized by the powder X-ray diffraction, X-ray photoelectron spectrometer, nitrogen adsorption isotherms, scanning electron microscopy, transmission electron microscopy, and UV-visible absorption spectra. The average length and the cross section diameter of the as-prepared samples were ca. 1.5 μm and ca. 80 nm, respectively. The photocatalytic activity was evaluated by photodegradation of methylene blue (MB) in aqueous solution. The N-doped mesoporous TiO2 nanorods showed an excellent photocatalytic activity, which may be attributed to the enlarged surface area (106.4 m2 g-1) and the narrowed band gap (2.05 eV). Besides, the rod-like photocatalyst was found to be easy to recycle. PMID:24428848

Biotechnology of enzyme has gained popularity due to the growing need for novel environmental technologies and the development of innovative mass-production. The work describes the original application of biosensors based on Penaeus merguiensis alkaline phosphatase (PM ALP) immobilized on gold nanorods (GNRs) to heavy metal determination. Penaeus merguiensis alkaline phosphatase (PM ALP) was immobilized on gold nanorods (GNRs) by ionic exchange and hydrophobic interactions. The optimum pH and temperature for maximum enzyme activity for the immobilized PM ALP are identified to be 11.0 and 60°C, respectively, for the hydrolysis of para-Nitrophenylphosphate (p-NPP). The kinetic studies confirm the Michaelis-Menten behavior and suggests overall slightly decrease in the performance of the immobilized enzyme with reference to the free enzyme. Km and Vmax values were 0.32µm and 54µm. min(-1) for free and 0.39µm and 48µmmin(-1) for immobilized enzymes, respectively. Similarly, the thermal stability, storage stability and stability at extreme pH of the enzyme is found to increase after the immobilization. The inhibitory effect heavy metal ions was studied on free and immobilized PM ALP. The bi-enzymatic biosensor were tested to study the influence of heavy metal ions and pesticides on the corresponding enzyme. The obtained high stability and lower decrease in catalytic efficiency suggested the great potential and feasibility of immobilized PM ALP nanobiocatalyst in efficient and apply the biosensor in total toxic metal content determination.

Incorporation of foreign moiety in the lattice of semiconductors significantly alters their optoelectronic behavior and opens a plethora of new applications. In this paper, we report the synthesis of sulfur-doped zinc oxide (S-doped ZnO) nanorods by reacting ZnO nanorods with diammonium sulfide in vapor phase. Microscopic investigation revealed that the morphological features, such as, the length (2-4 μm) and width (100-250 nm) of the original hexagonal ZnO nanorods remained intact post-sulfidation. X-ray photoelectron spectroscopy analysis of the sulfide sample confirmed the incorporation of sulfur into ZnO lattice. The optical measurements suggested the extension of absorption threshold into visible region upon sulfidation. Photoelectrochemical (PEC) activities of pure and S-doped ZnO nanorods were compared for water oxidation in visible light (λ > 420 nm), which showed several-fold increment in the performance of S-doped ZnO sample; the observed amelioration in the PEC activity was rationalized in terms of preferred visible light absorption and low resistance of sulfide sample, as evidenced by optical and electrochemical impedance spectroscopy.

Incorporation of foreign moiety in the lattice of semiconductors significantly alters their optoelectronic behavior and opens a plethora of new applications. In this paper, we report the synthesis of sulfur-doped zinc oxide (S-doped ZnO) nanorods by reacting ZnO nanorods with diammonium sulfide in vapor phase. Microscopic investigation revealed that the morphological features, such as, the length (2-4 μm) and width (100-250 nm) of the original hexagonal ZnO nanorods remained intact post-sulfidation. X-ray photoelectron spectroscopy analysis of the sulfide sample confirmed the incorporation of sulfur into ZnO lattice. The optical measurements suggested the extension of absorption threshold into visible region upon sulfidation. Photoelectrochemical (PEC) activities of pure and S-doped ZnO nanorods were compared for water oxidation in visible light (λ > 420 nm), which showed several-fold increment in the performance of S-doped ZnO sample; the observed amelioration in the PEC activity was rationalized in terms of preferred visible light absorption and low resistance of sulfide sample, as evidenced by optical and electrochemical impedance spectroscopy.

We have studied quantum coherence and interference phenomena in a quantum dot (QD)-metallicnanorod (MNR) hybrid system. Probe and control laser fields are applied to the hybrid system. Induced dipole moments are created in the QD and the MNR, and they interact with each other via the dipole-dipole interaction. Using the density matrix method, it was found that the power spectrum of MNR has two transparent, states and they can be switched to one transparent state by the control field. Ultrafast switching and sensing nanodevices could be produced using this model.

Novel thiol-functionalized mesoporous silica nanorods (MSNRs) were synthesized through a base co-condensation method, in which two organoalkoxysilanes, tetraethoxylsilane (TEOS) and bis[3-(triethoxysilyl)propyl]tetrasulfide (TESPT), were used as silica precursors simultaneously. TESPT was firstly used for both morphology control and inner surface functionalization of mesoporous silica hybrid materials. The microstructures as well as porous character of the MSNRs were characterized by means of SEM, XRD, TEM and N2 sorption measurements. Infrared spectrum analysis and heavy metal ions (Ag+ and Cd2+) adsorption measurements were carried out to confirm the functionalized framework of MSNRs.

As metalnanorods show much higher metal enhanced fluorescence (MEF) than metal nanospheres, microfluidic-based MEF is first explored with Ag nanorod (ND) arrays made by oblique angle deposition. By measuring the fluorescein isothiocyanate (FITC) solution sandwiched between the Ag NDs and a piece of cover slip, the enhancement factors (EFs) are found as 3.7 ± 0.64 and 6.74 ± 2.04, for a solution thickness at 20.8 μm and 10 μm, respectively. Because of the strong plasmonic coupling between the adjacent Ag NDs, only the emission of the fluorophores present in the three-dimensional NDs array gets enhanced. Thus, the corresponding effective enhancement factors (EEFs) are revealed to be relatively close, 259 ± 92 and 340 ± 102, respectively. To demonstrate the application of MEF in microfluidic systems, a multilayer of SiO2 NDs/Ag NDs is integrated with a capillary electrophoresis device. At a microchannel depth of 10 μm, an enhancement of 6.5 fold is obtained for amino acids separation detection. These results are very encouraging and open the possibility of MEF applications for the Ag ND arrays decorated microchannels. With the miniaturization of microfluidic devices, microfluidic-based MEF by Ag ND arrays will likely find more applications with further enhancement.

As metalnanorods show much higher metal enhanced fluorescence (MEF) than metal nanospheres, microfluidic-based MEF is first explored with Ag nanorod (ND) arrays made by oblique angle deposition. By measuring the fluorescein isothiocyanate (FITC) solution sandwiched between the Ag NDs and a piece of cover slip, the enhancement factors (EFs) are found as 3.7 ± 0.64 and 6.74 ± 2.04, for a solution thickness at 20.8 μm and 10 μm, respectively. Because of the strong plasmonic coupling between the adjacent Ag NDs, only the emission of the fluorophores present in the three-dimensional NDs array gets enhanced. Thus, the corresponding effective enhancement factors (EEFs) are revealed to be relatively close, 259 ± 92 and 340 ± 102, respectively. To demonstrate the application of MEF in microfluidic systems, a multilayer of SiO2 NDs/Ag NDs is integrated with a capillary electrophoresis device. At a microchannel depth of 10 μm, an enhancement of 6.5 fold is obtained for amino acids separation detection. These results are very encouraging and open the possibility of MEF applications for the Ag ND arrays decorated microchannels. With the miniaturization of microfluidic devices, microfluidic-based MEF by Ag ND arrays will likely find more applications with further enhancement.

Experimental and theoretical evidence has already suggested that the ferromagnetic metallic (FM) phase in colossal magnetoresistive manganites is not a conventional metal but rather a polaronic conductor. In the bilayer manganites La2-2xSr1+2xMn2O7 (LSMO), Angle Resolved Photoemission (ARPES) experiment revealed that the FM phase is a polaronic metal with a strong anisotropic character of the electronic excitations [1,2]. A small but well-defined quasiparticle (QP) with heavy mass along the [110] or ``nodal'' direction is found to account for the metallic properties and their temperature dependent evolution [2]. In this talk, we will discuss recent ARPES results on the x = 0.60 composition and contrast them to the x = 0.40 results. Recent work has shown that the region in proximity of x = 0.60 constitute the most metallic bilayer manganite with DC conductivity about one order of magnitude higher than that corresponding to the region 0.30 < x < 0.40. Much as in the x = 0.40 composition, for x = 0.60 along the nodal direction we observe a peak-dip-hump structure with QP of heavy effective mass. Quantitative differences in the electron-phonon coupling constant λ, the QP spectral weight and the hump energy are fully consistent with the doping evolution of the transport properties. [1] Nature 438, 474 (2005), [2] Phys. Rev. B 76, 233102 (2007).

High-speed stirring at elevated temperatures is shown to be effective in the symmetry-breaking process needed for the growth of the hard-to-synthesize silver nanorods from the polyol reduction of silver ions. This process competes with the facile formation of more symmetrical, spherical and cubic, nanoparticles. Once the seed is formed, further growth proceeds predominantly along the long axis, with a consequent increase of the particles' aspect ratio (that of the nanorod). When stirring is stopped shortly after seed formation, nanorods with a broad distribution of aspect ratios are obtained, while when the high-frequency stirring continues the distribution narrows significantly. The width of the nanorods can only be increased if the initial concentration of Ag(+) ions increases. Reducing the stirring speeds during seed formation lowers the yield of nanorods. Molecular dynamics simulations reveal that the formation of a nanometer-scale thin boundary region between a solid facet of the nanoparticle and the liquid around it, and the accommodation processes of metal (Ag) atoms transported through this boundary region from the liquid to the solid growth interface, are frustrated by sufficiently fast shear flow caused by high-frequency stirring. This arrests growth on seed facets parallel to the flow, leading, together with the preferential binding of the capping polymer to the (100) facet, to the observed growth in the (110) direction, resulting in silver nanorods capped at the ends by (111) facets and exposing (100) facets on the side walls.

Cu doping of ZnTe, which is an important semiconductor for various optoelectronic applications, has been successfully achieved previously by several techniques. However, besides its electrical transport characteristics, other physical and chemical properties of heavily Cu-doped ZnTe have not been reported. We found an interesting self-assembled formation of crystalline well-aligned Cu-Te nano-rods near the surface of heavily Cu-doped ZnTe thin films grown via the molecular beam epitaxy technique. A phenomenological growth model is presented based on the observed crystallographic morphology and measured chemical composition of the nano-rods using various imaging and chemical analysis techniques. When substitutional doping reaches its limit, the extra Cu atoms favor an up-migration toward the surface, leading to a one-dimensional surface modulation and formation of Cu-Te nano-rods, which explain unusual observations on the reflection high energy electron diffraction patterns and apparent resistivity of these thin films. This study provides an insight into some unexpected chemical reactions involved in the heavily Cu-doped ZnTe thin films, which may be applied to other material systems that contain a dopant having strong reactivity with the host matrix.

In this study, we report the synthesis of hierarchical chlorine-doped rutile TiO{sub 2} spherical clusters of nanorods photocatalyst on a large scale via a soft interface approach. This catalyst showed much higher photocatalytic activity than the famous commercial titania (Degussa P25) under visible light ({lambda}>420 nm). The resulting sample was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), nitrogen adsorption, X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectroscopy, {sup 1}H solid magic-angle spinning nuclear magnetic resonance (MAS-NMR) and photoluminescence spectroscopy. On the basis of characterization results, we found that the doping of chlorine resulted in red shift of absorption and higher surface acidity as well as crystal defects in the photocatalyst, which were the reasons for high photocatalytic activity of chlorine-doped TiO{sub 2} under visible light ({lambda}>420 nm). These hierarchical chlorine-doped rutile TiO{sub 2} spherical clusters of nanorods are very attractive in the fields of environmental pollutants removal and solar cell because of their easy separation and high activity. - Graphical abstract: Hierarchical chlorine-doped rutile TiO{sub 2} spherical clusters of nanorods photocatalyst were synthesized on a large scale via a soft interface approach. This catalyst showed much higher photocatalytic activity than the famous commercial titania (Degussa P25) under visible light ({lambda}>420 nm)

The Nb-doped TiO2 films were deposited on glass substrate at different Nb concentrations of 0 at.%, 1 at.%, 3 at.%, 5 at.% and 7 at.%, respectively and their electrical and structural properties were investigated. Subsequently, the Nb-doped TiO2 films were deposited on top of aligned ZnO Nanorod on ITO glass substrates using spin coating technique. The nanocomposited aligned ZnO nanorod/Nb-doped TiO2 (TiO2:Nb) were coated with different Nb concentrations of 0 at.%, 1 at.%, 3 at.%, 5 at.% and 7 at.%, respectively. The Dye-sensitized solar cells were fabricated from the nanocomposited aligned ZnO nanorod/TiO2:Nb photoanodes and their effects on the performance of the DSSCs were investigated. From the solar simulator measurement of DSSC the solar energy conversion efficiency (η) of 5.376% under AM 1.5 was obtained for the ZnO nanorod/TiO2:Nb-5at.%.

Spectrally and spatially resolved cathodoluminescence (CL) measurements were carried out at 80 K on undoped/Mg-doped GaN core-shell nanorods grown by selective area growth metalorganic vapor phase epitaxy in order to investigate locally the optical activity of the Mg dopants. A study of the luminescence emission distribution over the different regions of the nanorods is presented. We have investigated the CL fingerprints of the Mg incorporation into the non-polar lateral prismatic facets and the semi-polar facets of the pyramidal tips. The amount of Mg incorporation/activation was varied by using several Mg/Ga flow ratios and post-growth annealing treatment. For lower Mg/Ga flow ratios, the annealed nanorods clearly display a donor-acceptor pair band emission peaking at 3.26-3.27 eV and up to 4 LO phonon replicas, which can be considered as a reliable indicator of effective p-type Mg doping in the nanorod shell. For higher Mg/Ga flow ratios, a substantial enhancement of the yellow luminescence emission as well as several emission subbands are observed, which suggests an increase of disorder and the presence of defects as a consequence of the excess Mg doping.

Graded core/shell semiconductor nanorods and shaped nanorods are disclosed comprising Group II-VI, Group III-V and Group IV semiconductors and methods of making the same. Also disclosed are nanorod barcodes using core/shell nanorods where the core is a semiconductor or metal material, and with or without a shell. Methods of labeling analytes using the nanorod barcodes are also disclosed.

Graded core/shell semiconductor nanorods and shapped nanorods are disclosed comprising Group II-VI, Group III-V and Group IV semiconductors and methods of making the same. Also disclosed are nanorod barcodes using core/shell nanorods where the core is a semiconductor or metal material, and with or without a shell. Methods of labeling analytes using the nanorod barcodes are also disclosed.

The organization of semiconductor nanostructures into functional macroassemblies remains a fundamental challenge in nanoscience and nanotechnology. In the context of semiconductor epitaxial growth, efforts have focused on the application of advanced substrate patterning strategies for the directed assembly quantum-dot islands. We present a comprehensive investigation on the use of simple metal patterns to control the nucleation and growth of heteroepitaxial islands. In the Ge on Si model system, a square array of metal dots induces the assembly of Ge islands into an extensive two-dimensional lattice. The islands grow at sites between the metal dots and are characterized by unique shapes including truncated pyramids and nanorods, which are programmed prior to growth by the choices of metal species and substrate orientation. Our results indicate that ordering arises from the metal-induced oxidation of the Si surface; the oxide around each metal dot forms an array of periodic diffusion barriers that induce island ordering. The metals decorate the island surfaces and enhanced the growth of particular facets that are able to grow as a result of significant intermixing between deposited Ge and Si substrate atoms.

This paper proposes a novel design technique for realization of plasmonic logic gates. A 2D plasmonic all optical OR gate with the miniaturized size of 5 μm × 3 μm is presented. Ag metallic reflectors form the input and output waveguides to confine the light inside the gate. The logic operations are realized through selective propagation of light in the gate through hopping of the surface plasmon resonances along the metallicnanorods. With this novel idea approximately 100% of input signal propagates through the output waveguide and no division occurs at the cross point. Due to its simplicity, the OR gate was chosen to be the first implemented logic gate to verify the performance of the proposed method. Our proposed optical gate works at the operating wavelength of 652 nm with input signals of a transverse magnetic (TM) (Hz, Ex, Ey) polarized continuous wave with near zero cross talk between two input waveguides.

Surface modification of TiO2 film provides possibilities to improve photoelectrochemical (PEC) activity. In this study, we report on phosphate modified N/Si co-doped TiO2 nanorods films (Pi-N/Si-TiO2 NRs) for PEC water oxidation. Compared to the pristine TiO2 NRs, the Pi-N/Si-TiO2 NRs photoanode shows a 4.65-fold enhanced photocurrent density (1.44 mA cm-2) under light illumination. This significant improvement can be attributed to the synergistic effect of phosphate modification and the N and Si co-dopants. In addition to the improvement of ultraviolet and visible light response by N and Si co-dopants, phosphate modification is mainly responsible for charge transfer at the interface of the photoanode/electrolyte.

The thermal behavior of 1,2,4,5-tetracyanobenzene (TCNB), the synthesis of metal-2,3,9,10,16,17,23,24-octacyanophthalocyanine-metal [MPc(CN)8-M] (M = Cu, Fe, Ni) complexes by the tetramerization of TCNB, and the growth of MPc(CN)8-M nanorods were investigated. By chemical vapor deposition (CVD) in vacuum, MPc(CN)8 molecules were synthesized and MPc(CN)8-M nanorods were formed on all substrates. Among them, CuPc(CN)8 molecules were synthesized in high yield, and CuPc(CN)8-Cu nanorods were deposited uniformly and in high density, with diameters and lengths of 70-110 and 200-700 nm, respectively. The differences in the growth of MPc(CN)8-M nanorods were mainly attributed to the stability of the MPc(CN)8-M complex, the oxidation of ultrathin metal films, and the diffusion of metal atoms. Additionally, the tetramerization of TCNB by CVD at atmospheric pressure was performed on ultrathin Cu films, and the synthesis of CuPc(CN)8 molecules was observed by in situ UV-vis spectroscopy. CVD under atmospheric pressure is also useful for the synthesis of CuPc(CN)8 molecules.

In this paper crystalline noble metallicnanorods including Au and Ag with sub-10 nm diameter, are encapsulated within prealigned and open-ended multiwall carbon nanotubes (MWCNTs) through an electrodeposition method. As the external surface of CNTs has been insulated by the epoxy the CNT channel becomes the only path for the mass transport as well as the nanoreactor for the metal deposition. Highly crystallized Au and Ag2O nanorods parallel to the radial direction of CNTs are confirmed by high-resolution transmission electron microscopy, energy dispersive x-ray spectroscopy and x-ray powder diffraction spectroscopy. The Ag2O nanorods are formed by air oxidation on the Ag metals and show a single crystalline structure with (111) planes. The Au nanorods exhibit a complex crystalline structure including twin-crystal and lattice dislocation with (111) and (200) planes. These crystalline noble metallic nanostructures may have important applications for nanocatalysts for fuel cells as well as nanoelectronic and nanophotonic devices. This method is deemed to benefit the precise deposition of other crystalline nanostructures inside CNTs with a small diameter.

In this paper crystalline noble metallicnanorods including Au and Ag with sub-10 nm diameter, are encapsulated within prealigned and open-ended multiwall carbon nanotubes (MWCNTs) through an electrodeposition method. As the external surface of CNTs has been insulated by the epoxy the CNT channel becomes the only path for the mass transport as well as the nanoreactor for the metal deposition. Highly crystallized Au and Ag2O nanorods parallel to the radial direction of CNTs are confirmed by high-resolution transmission electron microscopy, energy dispersive x-ray spectroscopy and x-ray powder diffraction spectroscopy. The Ag2O nanorods are formed by air oxidation on the Ag metals and show a single crystalline structure with (111) planes. The Au nanorods exhibit a complex crystalline structure including twin-crystal and lattice dislocation with (111) and (200) planes. These crystalline noble metallic nanostructures may have important applications for nanocatalysts for fuel cells as well as nanoelectronic and nanophotonic devices. This method is deemed to benefit the precise deposition of other crystalline nanostructures inside CNTs with a small diameter.

Using first-principles calculations, we investigate the structural, electronic, and magnetic properties of 3d transition metal (TM) atoms substitutional doping of an arsenene monolayer. Based on the binding energy, the TM-substituted arsenene systems were found to be robust. Magnetic states were obtained for Ti, V, Cr, Mn and Fe doping. More importantly, a half-metallic state resulted from Ti and Mn doping, while the spin-polarized semiconducting state occurred with V, Cr and Fe doping. Our studies demonstrated the potential applications of TM-substituted arsenene for spintronics and magnetic storage devices.

TiO2 nanorod arrays (NRAs) were prepared on fluorine doped tin oxide (FTO) substrates by a facile two-step hydrothermal method. The nanorods were selectively grown on the FTO regions which were covered with TiO2 seeding layer. It took 5 h to obtain the compact arrays with the nanorod length of ~2 μm and diameter of ~50 nm. The photoelectrochemical (PEC) properties of TiO2 NRAs are also investigated. It is demonstrated that the TiO2 NRAs indicate the good photoelectric conversion ability with an efficiency of 0.22% at a full-wavelength irradiation. A photocurrent density of 0.21 mA/cm2 is observed at 0.7 V versus the saturated calomel electrode (SCE). More evidences suggest that the charge transferring resistance is lowered at an irradiation, while the flat-band potential ( V fb) is shifted towards the positive side.

Efforts to identify and develop new superconducting materials continue apace, motivated by both fundamental science and the prospects for application. For example, several new superconducting material systems have been developed in the recent past, including calcium-intercalated graphite compounds, boron-doped diamond and-most prominently-iron arsenides such as LaO(1-x)F(x)FeAs (ref. 3). In the case of organic superconductors, however, no new material system with a high superconducting transition temperature (T(c)) has been discovered in the past decade. Here we report that intercalating an alkali metal into picene, a wide-bandgap semiconducting solid hydrocarbon, produces metallic behaviour and superconductivity. Solid potassium-intercalated picene (K(x)picene) shows T(c) values of 7 K and 18 K, depending on the metal content. The drop of magnetization in K(x)picene solids at the transition temperature is sharp (<2 K), similar to the behaviour of Ca-intercalated graphite. The T(c) of 18 K is comparable to that of K-intercalated C(60) (ref. 4). This discovery of superconductivity in K(x)picene shows that organic hydrocarbons are promising candidates for improved T(c) values.

Crystallographic texture can have profound effects on the properties of a material. One method of texturing is through the application of an external magnetic field during processing. While this method works with highly magnetic systems, doping is required to couple non-magnetic systems with the external field. Experiments have shown that low concentrations of rare earth (RE) dopants in alumina powders have enabled this kind of texturing. The magnetic properties of RE elements are directly related to their f orbital, which can have as many as 7 unpaired electrons. Since d-block elements can have as many as 5 unpaired electrons the effects of substitutional doping of 3d transition metals (TM) for Al in alpha (stable) and theta (metastable) alumina on the local structure and magnetic properties, in addition to the energetic cost, have been calculated by performing first-principles calculations based on density functional theory. This study has led to the development of general guidelines for the magnetic moment distribution at and around the dopant atom, and the dependence of this distribution on the dopant atom type and its coordination environment. It is anticipated that these findings can aid in the selection of suitable dopants help to guide parallel experimental efforts. This project was supported in part by an internship at the Army Research Laboratory, administered by the Oak Ridge Institute for Science and Education, along with a grant of computer time from the DoD High Performance Computing Modernization Program.

In this study, vertically aligned Bi-doped TiO2 nanorod arrays as photoanodes were successfully grown on the fluorine-doped tin oxide by hydrothermal method. Structural analysis showed that bismuth was successfully incorporated into the TiO2 lattice at low concentration, but at higher concentration, phase segregation of Bi2O3 in the TiO2 matrix was occurred. TiO2 nanorods with 3 % bismuth concentration had minimum electrical resistivity. As the solid-state electrolyte, Mg-doped CuCrO2 nanoparticles with p-type conductivity were synthesized by sol-gel method. The fabricated all-oxide solid-state dye-sensitized solar cells with Bi-doped TiO2 nanorods displayed better photovoltaic performance due to the presence of Bi. The improved cell performance was correlated with the higher dye loading, slower charge recombination rate and the higher electrical conductivity of the photoanodes. After mechanical pressing, the all-oxide solid-state DSSC exhibited enhanced photovoltaic performance due to the formation of the large neck between adjacent nanoparticles by mechanical sintering. The open-circuit photovoltage decay measurement of the devices and electrical conductivity of the nanoparticles before and after pressing revealed that the mechanical pressing technique reduces charge recombination rate and facilitates electron transport through the interconnected nanoparticles.

To enhance electric fields around nanorods, a Ag nanorod-groove system is presented and its electric field distribution is studied using the finite difference time domain method. Since the superposition of the electric fields of the split multi-beam of light works as excitation for electron oscillations in the nanorods, enhanced electric fields occur around the nanorods. In addition, the effects of topological parameters of the nanorod-groove system, such as the oblique angle of the groove, displacement of the nanorod to the bottom of the groove, and separation between the nanorods on electric field distributions are also studied. These results may be helpful for designing substrates to obtain larger electric fields around nanorods.

In this study, we have fabricated and characterized the silicon [Si] wire solar cells with conformal ZnO nanorod antireflection coating [ARC] grown on a Al-doped ZnO [AZO] seed layer. Vertically aligned Si wire arrays were fabricated by electrochemical etching and, the p-n junction was prepared by spin-on dopant diffusion method. Hydrothermal growth of the ZnO nanorods was followed by AZO film deposition on high aspect ratio Si microwire arrays by atomic layer deposition [ALD]. The introduction of an ALD-deposited AZO film on Si wire arrays not only helps to create the ZnO nanorod arrays, but also has a strong impact on the reduction of surface recombination. The reflectance spectra show that ZnO nanorods were used as an efficient ARC to enhance light absorption by multiple scattering. Also, from the current-voltage results, we found that the combination of the AZO film and ZnO nanorods on Si wire solar cells leads to an increased power conversion efficiency by more than 27% compared to the cells without it. PMID:22222067

In this study, we have fabricated and characterized the silicon [Si] wire solar cells with conformal ZnO nanorod antireflection coating [ARC] grown on a Al-doped ZnO [AZO] seed layer. Vertically aligned Si wire arrays were fabricated by electrochemical etching and, the p-n junction was prepared by spin-on dopant diffusion method. Hydrothermal growth of the ZnO nanorods was followed by AZO film deposition on high aspect ratio Si microwire arrays by atomic layer deposition [ALD]. The introduction of an ALD-deposited AZO film on Si wire arrays not only helps to create the ZnO nanorod arrays, but also has a strong impact on the reduction of surface recombination. The reflectance spectra show that ZnO nanorods were used as an efficient ARC to enhance light absorption by multiple scattering. Also, from the current-voltage results, we found that the combination of the AZO film and ZnO nanorods on Si wire solar cells leads to an increased power conversion efficiency by more than 27% compared to the cells without it.

The immense pharmacological relevance of the herbal medicine curcumin including anti-cancer and anti-Alzheimer effects, suggests it to be a superior alternative to synthesised drugs. The diverse functionalities with minimal side effects intensify the use of curcumin not only as a dietary supplement but also as a therapeutic agent. Besides all this effectiveness, some recent literature reported the presence of deleterious heavy metal contaminants from various sources in curcumin leading to potential health hazards. In this regard, we attempt to fabricate ZnO based nanoprobes to detect metal conjugated curcumin. We have synthesized and structurally characterized the ZnO nanorods (NR). Three samples namely curcumin (pure), Zn-curcumin (non-toxic metal attached to curcumin) and Hg-curcumin (toxic heavy metal attached to curcumin) were prepared for consideration. The samples were electrochemically deposited onto ZnO surfaces and the attachment was confirmed by cyclic voltammetry experiments. Moreover, to confirm a molecular level interaction picosecond-resolved PL-quenching of ZnO NR due to Förster Resonance Energy Transfer (FRET) from donor ZnO NR to the acceptor curcumin moieties was employed. The attachment proximity of ZnO NR and curcumin moieties depends on the size of metals. First principles analysis suggests a variance of attachment sites and heavy metal Hg conjugated curcumin binds through a peripheral hydroxy group to NR. We fabricated a facile photovoltaic device consisting of ZnO NR as the working electrode with Pt counter electrode and iodide-triiodide as the electrolyte. The trend in photocurrent under visible light illumination suggests an enhancement in the case of heavy metal ions due to long range interaction and greater accumulation of charge at the active electrode. Our results provide a detailed physical insight into interfacial processes that are crucial for detecting heavy-metal attached phytomedicines and are thus expected to find vast

The enhancement of photoluminescence (PL) signals of CdSe nanorods caused by embedding in the cholesteric liquid crystals (CLCs) is demonstrated in this article. Three kinds of different CLCs have been used in this experiment, and the results have shown that the phenomenon of PL enhancement generally occurs in each sample. Moreover, the relations between the enhancement and the pitch of CLCs have been analyzed as well. It displays an inversely proportional property, that is, a greater enhancement of the PL signal is achieved in the samples with shorter pitches of CLCs. The highest PL amplification acquired in this study is 3.31 times. The enhancement phenomenon is attributed to the presence of oily streaks in CLCs, which possess advantages due to the excitation of CdSe nanorods. With the versatile properties that CLC have, this study suggests that the method could provide a potential way for PL signal manipulation in many optical fields.

Large-area "in situ" transition-metal substitution doping for chemical-vapor-deposited semiconducting transition-metal-dichalcogenide monolayers deposited on dielectric substrates is demonstrated. In this approach, the transition-metal substitution is stable and preserves the monolayer's semiconducting nature, along with other attractive characteristics, including direct-bandgap photoluminescence.

Ni doped ZnO (Zn1-xNixO, x=0.0, 0.03, 0.06 and 0.09) nanorods have been synthesized by Co-precipitation method. Zinc acetate dehydrate [Zn(CH3COO)2⋅2H2O], nickel nitrate [Ni(NO3)3⋅6H2O], sodium hydroxide and poly (vinyl pyrrolidone) (PVP) were mixed together. The morphology, optical and microstructure were determined by X-ray diffraction (XRD), scanning electron microscopy (SEM), Energy dispersive spectrum (EDS), atomic force microscopy (AFM), UV-DRS spectrum, photoluminescence spectra (PL) and Fourier transformer infrared spectroscopy (FT-IR). The presence of functional groups and chemical bonding is confirmed by FTIR. PL spectra of the Zn1-xNixO systems shows that the shift in near band edge (NBE) UV emission from 321 to 322 nm and a shift in red band (RB) emission from 620 to 631 nm which conforms the substitution of Ni into the ZnO lattice. The investigation conformed that the products were of the wurtzite structure of ZnO. The hexagonal nanorods have edge length 31 nm and thickness of 39 nm. EDS result showed that the amount of Ni in the product is about 9%, these Ni doped hexagonal nanorods exhibits a blue shifts and weak (UV) emission peak, compared with pure ZnO, which may be induced by the Ni-doping different concentrations 0.0, 0.3, 0.6 and 0.9 M. The growth mechanism of the doped hexagonal nanorods was also discussed.

Metallic nanoparticles (such as gold and silver) have been intensely studied for wound healing applications due to their ability to be easily functionalized, possess antibacterial properties, and their strong potential for targeted drug release. In this study, rod-shaped silver nanorods (AgNRs) and gold nanorods (AuNRs) were fabricated by electron beam physical vapor deposition (EBPVD), and their cytotoxicity toward human skin fibroblasts were assessed and compared to sphere-shaped silver nanospheres (AgNSs) and gold nanospheres (AuNSs). Results showed that the 39.94 nm AgNSs showed the greatest toxicity with fibroblast cells followed by the 61.06 nm AuNSs, ∼556 nm × 47 nm (11.8:1 aspect ratio) AgNRs, and the ∼534 nm × 65 nm (8.2:1 aspect ratio) AuNRs demonstrated the least amount of toxicity. The calculated IC50 (50% inhibitory concentration) value for the AgNRs exposed to fibroblasts was greater after 4 days of exposure (387.3 μg mL(-1)) compared to the AgNSs and AuNSs (4.3 and 23.4 μg mL(-1), respectively), indicating that these spherical metallic nanoparticles displayed a greater toxicity to fibroblast cells. The IC50 value could not be measured for the AuNRs due to an incomplete dose response curve. The reduced cell toxicity with the presently developed rod-shaped nanoparticles suggests that they may be promising materials for use in numerous biomedical applications.

This paper reports the detail description of the structural and thermoluminescence of the RE3+-doped (RE=Eu, Tb) ZnO nanorods prepared by adopting co-precipitation method. Formation of as synthesized ZnO nanorods were confirmed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The XRD pattern showed monophasic nature of the as prepared ZnO doped with Eu3+ and Tb3+ ions. The SEM image elaborates the nanorod morphology of RE3+ doped ZnO with diameter ranging between 60-90 nm and length between 600-900 nm. The thermoluminescence spectra of the X-ray irradiated ZnO:Eu3+ and ZnO:Tb3+ show the prominent peak for the broad glow curve peaked at 365 °C and 350 °C, respectively, which have been generated via the recombination of the released electrons from the traps upon thermal stimulation. The peaks are found to obey first order kinetics and the activation energy for the ZnO:Eu3+ and ZnO:Tb3+ samples, estimated via isothermal luminescence glow peak decay method, are found to be 0.8 eV and 0.9 eV respectively. Furthermore, the TL dose response and reproducibility were also studied in details, which could be very useful to establish the potentiality of the present phosphors in the field of radiation dosimetry.

A method of synthesizing metaldoped carbon films by placing a substrate in a chamber with a selected amount of a metalorganic compound. An electron cyclotron resonance is applied to the chamber in order to vaporize the metalorganic compound. The resonance is applied to the chamber until a metaldoped carbon film is formed. The metalorganic compound is preferably selected from the group consisting of an organic salt of ruthenium, palladium, gold or platinum.

To probe the origin of p-type conductivity in Sb-doped ZnO, a careful and detailed synchrotron radiation study was performed. The extended X-ray absorption fine structure and X-ray photoelectron spectroscopy investigations provided the evidence for the formation of the complex defects comprising substitution Sb ions at Zn sites (Sb{sub Zn}) and Zn vacancies within the Sb-doped ZnO lattice. Such complex defects result in the increases of Sb-O coordination number and the Sb valence and thereby lead to the p-type conductivity of Sb-doped ZnO. The back-gate field-effect-transistors based on single nanorod of Sb-doped ZnO were constructed, and the stable p-type conduction behavior was confirmed.

Doped semiconductor nanocrystals (d-dots), specifically ones not containing heavy metal ions, have the potential to become a class of mainstream emissive materials. Mn- and Cu-doped ZnSe or ZnS d-dots can cover an emission window similar to that of the current workhorse of intrinsic quantum dot (q-dots) emitters, CdSe nanocrystals. We synthesized high quality stable Cu doped ZnSe in nonpolar as well as polar solvent. The emission intensity of these doped nanocrystals is found stable for months under UV irradiation, after different multifunctional ligand which is important for any biological detection. We have also synthesized the stable Mn doped ZnS in nonpolar solvent more than 50% QY.. The doped nanocrystals are characterized by TEM, XRD, EPR and ICP analysis.

Herein we report the influence of a ZrO2 underlayer on the PEC (photoelectrochemical) behavior of hematite nanorod photoanodes for efficient solar water splitting. Particular attention was given to the cathodic shift in onset potential and photocurrent enhancement. Akaganite (β-FeOOH) nanorods were grown on ZrO2-coated FTO (fluorine-doped tin oxide) substrates. Sintering at 800 °C transformed akaganite to the hematite (α-Fe2O3) phase and induced Sn diffusion into the crystal structure of hematite nanorods from the FTO substrates and surface migration, shallow doping of Zr atoms from the ZrO2 underlayer. The ZrO2 underlayer-treated photoanode showed better water oxidation performance compared to the pristine (α-Fe2O3) photoanode. A cathodic shift in the onset potential and photocurrent enhancement was achieved by surface passivation and shallow doping of Zr from the ZrO2 underlayer, along with Sn doping from the FTO substrate to the crystal lattice of hematite nanorods. The Zr based hematite nanorod photoanode achieved 1 mA/cm(2) at 1.23 VRHE with a low turn-on voltage of 0.80 VRHE. Sn doping and Zr passivation, as well as shallow doping, were confirmed by XPS, Iph, and M-S plot analyses. Electrochemical impedance spectroscopy revealed that the presence of a ZrO2 underlayer decreased the deformation of FTO substrate, improved electron transfer at the hematite/FTO interface and increased charge-transfer resistance at the electrolyte/hematite interface. This is the first systematic investigation of the effects of Zr passivation, shallow doping, and Sn doping on hematite nanorod photoanodes through application of a ZrO2 underlayer on the FTO substrate.

Eu3+ ions doped LaBWO6 phosphors were synthesized by a facile hydrothermal method. The phase, morphology and luminescence properties of the obtained samples were characterized. The XRD, Raman and IR results showed that the obtained samples have the orthorhombic phase, indicating the doped Eu3+ will not change the phase of host. The TEM and SEM images showed that the obtained sample have the rod-like morphology. The excitation spectrum showed that Eu3+ ions doped LaBWO6 phosphors have excitation bands ranging from the ultraviolet region to blue region. The emission spectra showed that Eu3+ ions doped LaBWO6 phosphors emit dominate red light under 281, 394 and 464 nm excitations. And the decay of the red emission fitted well with the double exponential function.

We study biological sensing using plasmonic and photonic-plasmonic resonances of arrays of long metallicnanorods and analyze the impact of these resonances on emission dynamics of quantum dot bioconjugates. We demonstrate that the localized surface plasmon resonances (LSPRs) and plasmonic lattice modes of such arrays can be used to detect a single self-assembled monolayer of alkanethiol at the visible (550 nm) and near infrared (770 nm) range with well resolved shifts. We study the adsorption of streptavidin-quantum dot conjugates to this monolayer, demonstrating that formation of nearly two dimensional arrays of quantum dots with limited emission blinking can lead to extra well-resolved wavelength shifts in these modes. Using spectrally-resolved lifetime measurements, we study the emission dynamics of such quantum dot bioconjugates within their monodispersed size distribution. We show that, despite their close vicinity to the nanorods, the rate of energy transfer from these quantum dots to nanorods is rather weak, while the plasmon field enhancement can be strong. Our results reveal that the nanorods present a strong wavelength or size-dependent non-radiative decay channel to the quantum dot bioconjugates.

The present invention generally relates to binary or higher order semiconductor nanoparticles doped with a metallic element, and thermoelectric compositions incorporating such nanoparticles. In one aspect, the present invention provides a thermoelectric composition comprising a plurality of nanoparticles each of which includes an alloy matrix formed of a Group IV element and Group VI element and a metallic dopant distributed within the matrix.

Simple method was developed for doping refractory metals with oxygen. The metal specimens are heated in a dynamic high-vacuum system. The system can be used for other oxygen absorption processes /such as low-pressure oxidation measurements/ and for gases other than oxygen.

The present invention generally relates to binary or higher order semiconductor nanoparticles doped with a metallic element, and thermoelectric compositions incorporating such nanoparticles. In one aspect, the present invention provides a thermoelectric composition comprising a plurality of nanoparticles each of which includes an alloy matrix formed of a Group IV element and Group VI element and a metallic dopant distributed within the matrix.

Illumination of noble metal nanoparticles at the plasmon resonance causes substantial heat generation, and the transient and highly localized temperature increases that result from this energy conversion can be exploited for photothermal therapy by plasmonically heating gold nanorods (NRs) bound to cell surfaces. Here, plasmonic heating is used for the first time to locally release silver from gold core/silver shell (Au@Ag) NRs targeted to bacterial cell walls. A novel biomimetic method of preparing Au@Ag core-shell NRs is employed, involving deposition of a thin organic polydopamine (PD) primer onto Au NR surfaces, followed by spontaneous electroless silver metallization, and conjugation of antibacterial antibodies and passivating polymers for targeting to gram-negative and gram-positive bacteria. Dramatic cytotoxicity of S. epidermidis and E. coli cells targeted with Au@Ag NRs is observed upon exposure to light as a result of the combined antibacterial effects of plasmonic heating and silver release. The antibacterial effect is much greater than with either plasmonic heating or silver alone, implying a strong therapeutic synergy between cell-targeted plasmonic heating and the associated silver release upon irradiation. The findings suggest a potential antibacterial use of Au@Ag NRs when coupled with light irradiation, which has not been previously described.

A novel enzyme-induced metallization colorimetric assay is developed to monitor and measure beta-galactosidase (β-gal) activity, and is further employed for colorimetric bacteriophage (phage)-enabled detection of Escherichia coli (E. coli). This assay relies on enzymatic reaction-induced silver deposition on the surface of gold nanorods (AuNRs). In the presence of β-gal, the substrate p-aminophenyl β-d-galactopyranoside is hydrolyzed to produce p-aminophenol (PAP). Reduction of silver ions by PAP generates a silver shell on the surface of AuNRs, resulting in the blue shift of the longitudinal localized surface plasmon resonance peak and multicolor changes of the detection solution from light green to orange-red. Under optimized conditions, the detection limit for β-gal is 128 pM, which is lower than the conventional colorimetric assay. Additionally, the assay has a broader dynamic range for β-gal detection. The specificity of this assay for the detection of β-gal is demonstrated against several protein competitors. Additionally, this technique is successfully applied to detect E. coli bacteria cells in combination with bacteriophage infection. Due to the simplicity and short incubation time of this enzyme-induced metallization colorimetric method, the assay is well suited for the detection of bacteria in low-resource settings.

As metal nano-arrays show great potential on metal enhanced fluorescence (MEF) than random nanostructures, MEF of Ag zigzag nanorod (ZNR) arrays made by oblique angle deposition has been studied for biomolecule-protein interaction and DNA hybridization. By changing the folding number and the deposition substrate temperature, a 14-fold enhancement factor (EF) is obtained for biotin-neutravidin detection. The optimal folding number is decided as Z=7, owing to the high scattering intensity of Ag ZNRs. The substrate temperature T=25°C and 0°C slightly alters the morphology of Ag ZNRs but has no big difference in EF. Further, Ag ZNRs deposited on a layer of Ag film have been introduced to the DNA hybridization and a significant signal enhancement has been observed through the fluorescence microscope. Through a detailed quantitative EF analysis, which excludes the enhancing effect from the increased surface area of ZNRs and only considers the contribution of MEF, an EF of 28 is achieved for the hybridization of two single-stranded oligonucleotides with 33 bases. Furthermore, a limit of detection is determined as 0.01pM. We believe that the Ag ZNR arrays can serve as a universal and sensitive bio-detection platform.

Illumination of noble metal nanoparticles at the plasmon resonance causes substantial heat generation, and the transient and highly localized temperature increases that result from this energy conversion can be exploited for photothermal therapy by plasmonically heating gold nanorods (NRs) bound to cell surfaces. Here, we report the first use of plasmonic heating to locally release silver from gold core/silver shell (Au@Ag) NRs targeted to bacterial cell walls. A novel biomimetic method of preparing Au@Ag core-shell NRs was employed, involving deposition of a thin organic polydopamine (PD) primer onto Au NR surfaces, followed by spontaneous electroless silver metallization, and conjugation of antibacterial antibodies and passivating polymers for targeting to gram-negative and gram-positive bacteria. Dramatic cytotoxicity of S. epidermidis and E. coli cells targeted with Au@Ag NRs was observed upon exposure to light as a result of the combined antibacterial effects of plasmonic heating and silver release. The antibacterial effect was much greater than with either plasmonic heating or silver alone, implying a strong therapeutic synergy between cell-targeted plasmonic heating and the associated silver release upon irradiation. Our findings suggest a potential antibacterial use of Au@Ag NRs when coupled with light irradiation, which was not previously described. PMID:23847147

Organic superconductors have π-molecular orbitals, from which electrons can become delocalized, giving rise to metallic conductivity due to orbital overlap between adjacent molecules. Here we report the discovery of superconductivity at a transition temperature (T(c)) of ~5 K in alkali-metal-doped phenanthrene. A 1-GPa pressure leads to a 20% increase of T(c), suggesting that alkali-metal-doped phenanthrene shows unconventional superconductivity. Raman spectra indicate that alkali-metaldoping injects charge into the system to realize the superconductivity. The discovery of superconductivity in A(3)phenanthrene (where A can be either K or Rb) produces a novel broad class of superconductors consisting of fused hydrocarbon benzene rings with π-electron networks. An increase of T(c) with increasing number of benzene rings from three to five suggests that organic hydrocarbons with long chains of benzene rings are potential superconductors with high T(c).

Bamboo-like WO3 nanorods were anchored on three-dimensional nitrogen-doped graphene frameworks (r-WO3/3DNGF) by a facile one-step hydrothermal synthesis plus heating processes. There is a strong dependence of the obtained r-WO3/3DNGF nanostructures on the content of 3DNGF. The composite with 20 wt% 3DNGF content shows the most favorable structure where bamboo-like WO3 nanorods lie flat on the surface of fungus-like 3DNGF, and exhibits a high discharge capacity of 828 mAh g-1 over 100 cycles at 80 mA g-1 with the largest capacity retention of 73.9% for WO3 and excellent rate capacities of 719, 665, 573, 453 and 313 mAh g-1 at 80, 160, 400, 800 and 1600 mA g-1, respectively. The electrochemical performance is better than most of reported WO3-based carbonaceous composites, which can be attributed to the synergistic effects of the following actions: i) WO3 nanorods effectively shorten the diffusion path of Li+; ii) mechanically strong 3DNGF alleviates the huge volume change of WO3 upon Li+ intercalation/extraction; and iii) nitrogen-doping in 3D graphene frameworks improves electronic conductivity and provides large numbers of lithium ion diffusion channels.

Organic foams having a low density and very small cell size and method for roducing same in either a metal-loaded or unloaded (nonmetal loaded) form are described. Metal-doped foams are produced by soaking a polymer gel in an aqueous solution of desired metal salt, soaking the gel successively in a solvent series of decreasing polarity to remove water from the gel and replace it with a solvent of lower polarity with each successive solvent in the series being miscible with the solvents on each side and being saturated with the desired metal salt, and removing the last of the solvents from the gel to produce the desired metal-doped foam having desired density cell size, and metal loading. The unloaded or metal-doped foams can be utilized in a variety of applications requiring low density, small cell size foam. For example, rubidium-doped foam made in accordance with the invention has utility in special applications, such as in x-ray lasers.

Employing Nernst-Einstein decomposition σ =e2χcD of the conductivity σ onto charge susceptibility (compressibility) χc and diffusion constant D , we argue that the bad-metallic behavior of σ in the regime of high temperatures and lightly doped insulator is dominated by the strong temperature and doping dependence of χc. In particular, we show how at small dopings χc strongly decreases towards undoped-insulating values with increasing temperature and discuss a simple picture leading to the linear-in-temperature resistivity with the prefactor increasing inversely with decreasing concentration (p ) of doped holes, ρ ∝T /p . On the other hand, D shows weak temperature and doping dependence in the corresponding regime. We support our arguments by numerical results on the two-dimensional Hubbard model and discuss the proposed picture from the experimental point of view.

Pure and Co-doped zinc oxide nanomaterials were prepared by a simple low temperature synthesis and were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution-transmission electron microscopy (HR-TEM), diffused reflectance spectroscopy (DRS) and electron paramagnetic resonance (EPR) techniques. The results showed the formation of nanobushes that consists of several nanowires for pure ZnO and the nanorods formed by self-aggregation for Co-doped ZnO. The presence of Co{sup 2+} ions replacing some of the Zn{sup 2+} in the ZnO lattice was confirmed by EPR and DRS studies. The mechanism for the formation of self-aggregated and self-aligned ZnO rods after the incorporation of cobalt in the lattice by the building block units is discussed in this study. Morphological studies were carried out using SEM and HR-TEM, which supports the validity of the proposed mechanism for the formation of ZnO nanobushes and Co-doped ZnO nanorods. The synthesized nanomaterials were found to have good optoelectronic properties.

The polymer nanocomposite thin film is of interest due to many advantages for electromagnetic interference (EMI) shielding. In this work, low temperature (‑30 ± 2 °C) in situ synthesized polyaniline (PANI)–MnO2 nanorod composite (PMN) were solution processed, followed by acid vapor treatment for preparing free standing films and EMI shielding effectiveness (SE) were investigated in the frequency range i.e. X-band (8.2–12.4 GHz) and Ku-band (12.4–18 GHz). As prepared PMN film (169 ± 2 µm) shows most effective EMI SE ~ 35 dB (EMI shielding due to absorption, SEA ~ 24 dB and EMI shielding due to reflection SER ~ 11 dB) in the X-band which was observed to be ~39 dB (SEA ~ 29 dB and SER ~ 10 dB) in the Ku-band. The variations of conductivity, penetration depth, EM attenuation constant of the PMN film in the X-band and Ku-band were also investigated along with dielectric study.

We synthesized ZnO nanorods (NRs) using simple hydrothermal method, with the simultaneous incorporation of gallium (Ga) and indium (In), in addition, investigated the co-doping effect on the morphology, microstructure, electronic structure, and electrical/optical properties. The growth behavior of the doped NRs was affected by the nuclei density and polarity of the (001) plane. The c-axis parameter of the co-doped NRs was similar to that of undoped NRs due to the compensated lattice distortion caused by the presence of dopants that are both larger (In3+) and smaller (Ga3+) than the host Zn2+ cations. Red shifts in the ultraviolet emission peaks were observed in all doped NRs, owing to the combined effects of NR size, band gap renormalization, and the presence of stacking faults created by the dopant-induced lattice distortions. In addition, the NR/p-GaN diodes using co-doped NRs exhibited superior electrical conductivity compared to the other specimens due to the increase in the charge carrier density of NRs and the relatively large effective contact area of (001) planes. The simultaneous doping of In and Ga is therefore anticipated to provide a broader range of optical, physical, and electrical properties of ZnO NRs for a variety of opto-electronic applications.

We synthesized ZnO nanorods (NRs) using simple hydrothermal method, with the simultaneous incorporation of gallium (Ga) and indium (In), in addition, investigated the co-doping effect on the morphology, microstructure, electronic structure, and electrical/optical properties. The growth behavior of the doped NRs was affected by the nuclei density and polarity of the (001) plane. The c-axis parameter of the co-doped NRs was similar to that of undoped NRs due to the compensated lattice distortion caused by the presence of dopants that are both larger (In3+) and smaller (Ga3+) than the host Zn2+ cations. Red shifts in the ultraviolet emission peaks were observed in all doped NRs, owing to the combined effects of NR size, band gap renormalization, and the presence of stacking faults created by the dopant-induced lattice distortions. In addition, the NR/p-GaN diodes using co-doped NRs exhibited superior electrical conductivity compared to the other specimens due to the increase in the charge carrier density of NRs and the relatively large effective contact area of (001) planes. The simultaneous doping of In and Ga is therefore anticipated to provide a broader range of optical, physical, and electrical properties of ZnO NRs for a variety of opto-electronic applications. PMID:28155879

In this paper, we first incorporated Al(NO3)3·9H2O as the Al source into ZnO nanorods (NRs) lattice via the hydrothermal method to modify nature properties of ZnO NRs for the fabrication of perovskite solar cells (PSCs). The X-ray diffraction (XRD) pattern of Al-doped ZnO NRs exhibits higher 2θ values and stronger intensity of (002) plane. Larger optical band gap and higher electrical conductivity of Al-doped ZnO NRs are also observed relative to non-doped ZnO ones. The steady-state photoluminescence shows effective charge extraction and collection at the interface between Al-doped ZnO NRs and perovskite layer. The optimized PSC based on Al-doped ZnO NRs showed an open-circuit voltage of 0.84 V, a short-circuit current density of 21.93 mA/cm2, a fill factor of 57%, and a power conversion efficiency of 10.45% that was 23% higher than the non-doped ZnO ones.

This paper describes a facile method for the synthesis of Au/AuAg/Ag2S/PbS core-multishell nanorods with double trapping layers. The synthesis, in sequence, involved deposition of Ag shells onto the surfaces of Au nanorod seeds, formation of AuAg shells by a galvanic replacement reaction, and overgrowth of the Ag2S shells and PbS shells. The resulting core-multishell nanorod possesses an air gap between the Au core and the AuAg shell. Together with the Ag2S shell, the air gap can efficiently trap light, causing strong field confinement and nonlinear enhancement. The as-prepared Au/AuAg/Ag2S/PbS core-multishell nanorods display distinct localized surface plasmon resonance and nonlinear optical properties, demonstrating an effective pathway for maneuvering the optical properties of nanocavities.

The spin-dependent electronic structures of aluminum-(Al) doped zigzag silicene nanoribbons (ZSiNRs) are investigated by first-principles calculations. When ZSiNRs are substitutionally doped by a single Al atom on different sites in every three primitive cells, they become half-metallic in some cases, a property that can be used in spintronic devices. More interestingly, spin-down electrons can be transported at the Fermi energy when the Al atom is placed on the sub-edge site. In contrast, spin-up electrons can be transported at the Fermi energy when the ZSiNRs are doped on sites near their centre. The magnetic moment on the edge is considerably suppressed if the Al atom is doped on edge or near-edge sites. Similar results are obtained for a phosphorus-(P) and boron-(B) doped ZSiNR. When two or more Si atoms are replaced by Al atoms, in general the half-metallic behaviour is replaced by a metallic, spin gapless semiconducting or semiconducting one. When a line of six Si atoms, along the ribbon's width, are replaced by Al atoms, the spin resolution of the band structure is suppressed and the system becomes nonmagnetic.

This paper describes a facile method for the synthesis of Au/AuAg/Ag2S/PbS core-multishell nanorods with double trapping layers. The synthesis, in sequence, involved deposition of Ag shells onto the surfaces of Au nanorod seeds, formation of AuAg shells by a galvanic replacement reaction, and overgrowth of the Ag2S shells and PbS shells. The resulting core-multishell nanorod possesses an air gap between the Au core and the AuAg shell. Together with the Ag2S shell, the air gap can efficiently trap light, causing strong field confinement and nonlinear enhancement. The as-prepared Au/AuAg/Ag2S/PbS core-multishell nanorods display distinct localized surface plasmon resonance and nonlinear optical properties, demonstrating an effective pathway for maneuvering the optical properties of nanocavities.This paper describes a facile method for the synthesis of Au/AuAg/Ag2S/PbS core-multishell nanorods with double trapping layers. The synthesis, in sequence, involved deposition of Ag shells onto the surfaces of Au nanorod seeds, formation of AuAg shells by a galvanic replacement reaction, and overgrowth of the Ag2S shells and PbS shells. The resulting core-multishell nanorod possesses an air gap between the Au core and the AuAg shell. Together with the Ag2S shell, the air gap can efficiently trap light, causing strong field confinement and nonlinear enhancement. The as-prepared Au/AuAg/Ag2S/PbS core-multishell nanorods display distinct localized surface plasmon resonance and nonlinear optical properties, demonstrating an effective pathway for maneuvering the optical properties of nanocavities. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr09151a

This study focuses on the effect of annealing the Au seed layer (ASL) on the structural and optical properties of electrodeposited ZnO nanorods. ZnO nanorods were fabricated in a three-step approach. In the first step, ASLs were deposited using an ion sputter technique. In the second step, layers were annealed in air at various temperatures ranging from 400 degrees C to 600 degrees C. Finally, ZnO nanorods were grown using an electrodeposition method. The field-emission scanning electron microscopy analysis showed that better aligned ZnO nanorods are fabricated on the annealed ASL compared with non-annealed ASL The X-ray diffraction analysis showed a notable improvement in directional growth along the (002) crystallographic plane when ZnO nanorods were grown on the annealed ASL. The photoluminescence analysis showed that the UV emission peak of ZnO nanorods on the annealed ASL at 400 degrees C was blue-shifted and increased.

A novel asymmetric supercapacitor device for energy storage is fabricated using K0.3WO3 nanorods as negative electrode and nitrogen-doped porous carbon (CBC-1) based on agricultural wastes corn bract as positive electrode. The K0.3WO3 nanorods are composed of some thinner needle-shaped nanorods which are parallel to each other, and the CBC-1 reveals rough surface of coral-like frameworks with abundant nanopores. The structures can provide high surface area, low diffusion paths and intercalation/de-intercalation of electrolyte ions between the electrode/electrolyte interfaces. Thus, the asymmetric supercapacitor exhibits high energy density about 26.3 Wh kg-1 at power density of 404.2 W kg-1 in the wide voltage region of 0-1.6 V, as well as a good electrochemical stability (80% capacitance retention after 1000 cycles). Such outstanding electrochemical behaviors imply the CBC-1//K0.3WO3 asymmetric supercapacitor is a promising practical energy-storage system.

Dopingmetal oxide charge transport material with an organic molecule lowers electrical resistance while maintaining transparency and thus is optimal for use as charge transport materials in various organic optoelectronic devices such as organic photovoltaic devices and organic light emitting devices.

It has been shown that diluted magnetic semiconductors could form by hole doping into ZnO(T.Dietl, et al.,) Science 287, 1019(2000). In this work doping by non-magnetic Cu into ZnO has been simulated by the accurate ab initio FLAPW method(E.Wimmer, H.Krakauer, M.Weinert, and A.J.Freeman, Phys. Rev. B 24), 864(1981), and references therein, using GGA to represent the exchange-correlation potential. For a 1/8 doping concentration which is simulated by a 16 atom supercell, we find magnetic moments of 0.58 μB on Cu, and 0.08 μB or 0.05 μB on neighboring O. Decreasing the doping concentration to 1/16 causes the magnetic moments change by 0.005 μ_B. In the ferromagnetic (FM) phase, the system is half-metallic. The hole states on the Fermi surface are mainly determined by Cu 3d and O 2p hybridization. The calculated exchange splitting is 0.45 eV which opens a half-metallic gap of 0.30 eV. For comparison with the FM phase, several anti-ferromagnetic (AFM) phases are being investigated using the doubled supercell. To design possible diluted magnetic semiconductors, simulations of doping by other non-magnetic ions into ZnO are also in progress.

Transition metaldoped zinc oxide has been studied recently due to its potential application in spintronic devices. The magnetic semiconductor, often called Diluted Magnetic Semiconductors (DMS), has the ability to incorporate both charge and spin into a single formalism. Despite a large number of studies on ferromagnetism in ZnO based DMS and the realization of its room temperature ferromagnetism, there is still a debate about the origin of the ferromagnetism. In this work, the synthesis and characterization of transition metaldoped zinc oxide have been carried out. The sol-gel method was used to synthesize thin films, and they were subsequently annealed in air. Characterization of doped zinc oxide films was carried out using the UV-visible range spectrometer, scanning electron microscopy, superconducting quantum interference device (SQUID), x-ray diffraction(XRD) and positron annihilation spectroscopy. Hysteresis loops were obtained for copper and manganese doped zinc oxide, but a reversed hysteresis loop was observed for 2% Al 3% Co doped zinc oxide. The reversed hysteresis loop has been explained using a two-layer model.

A novel and efficient CeO2-doped MnO2 nanorods decorated reduced graphene oxide (CeO2-MnO2/RGO) nanocomposite was successfully synthesized via hydrothermal method. The growth of the CeO2 doped MnO2 nanorods over GO sheets and reduction of GO were simultaneously carried out under hydrothermal treatment. The morphology and structure of as-synthesized nanocomposite were characterized by field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and Raman spectroscopy, which revealed the formation of CeO2-MnO2 decorated RGO nanocomposites. The electrochemical performance of as-prepared CeO2-MnO2/RGO nanocomposites as an active electrode material for supercapacitor was evaluated by cyclic voltammetry, charge-discharge, and electrochemical impedance spectroscopy (EIS) methods in 2M alkaline medium. The obtained results revealed that as-synthesized CeO2-MnO2/RGO nanocomposite exhibited higher specific capacitance (648F/g) as compared to other formulations (MnO2/RGO nanocomposites: 315.13 F/g and MnO2 nanorods: 228.5 F/g) at the scan rate of 5mV/s. After 1000 cycles, it retained ∼90.4%, exhibiting a good stability. The high surface area, enhanced electrical conductivity, and good stability possess by the nanocomposite make this material a promising candidate to be applied as a supercapacitor electrode.

In this work, an environmental friendly RC/N-TiO2 nanocomposite thin film was designed as a green portable photocatalyst by utilizing recycled newspaper as sustainable cellulose resource. Investigations on the influence of N-doped TiO2 nanorods incorporation on the structural and morphological properties of RC/N-TiO2 nanocomposite thin film are presented. The resulting nanocomposite thin film was characterized by FESEM, AFM, FTIR, UV-vis-NIR spectroscopy, and XPS analysis. The results suggested that there was a remarkable compatibility between cellulose and N-doped TiO2 nanorods anchored onto the surface of the RC/N-TiO2 nanocomposite thin film. Under UV and visible irradiation, the RC/N-TiO2 nanocomposite thin film showed remarkable photocatalytic activity for the degradation of methylene blue solution with degradation percentage of 96% and 78.8%, respectively. It is crucial to note that the resulting portable photocatalyst produced via an environmental and green technique in its fabrication process has good potential in the field of water and wastewater treatment application.

To fully deploy the potential of semiconductor nanocrystal films as low-cost electronic materials, a better understanding of the amount of dopants required to make their conductivity metallic is needed. In bulk semiconductors, the critical concentration of electrons at the metal-insulator transition is described by the Mott criterion. Here, we theoretically derive the critical concentration nc for films of heavily doped nanocrystals devoid of ligands at their surface and in direct contact with each other. In the accompanying experiments, we investigate the conduction mechanism in films of phosphorus-doped, ligand-free silicon nanocrystals. At the largest electron concentration achieved in our samples, which is half the predicted nc, we find that the localization length of hopping electrons is close to three times the nanocrystals diameter, indicating that the film approaches the metal-insulator transition.

Pt/ZnO nanorod (NR) and Pt/modified ZnO NR Schottky barrier ultraviolet (UV) photodetectors (PDs) were prepared with different seed layers and metal oxide modifying layer materials. In this paper, we discussed the effect of metal oxide modifying layer on the performance of UV PDs pre- and post-deposition annealing at 300°C, respectively. For Schottky barrier UV PDs with different seed layers, the MgZnO seed layer-PDs without metal oxide coating showed bigger responsivity and larger detectivity (Dλ*) than those of PDs with ZnO seed layer, and the reason was illustrated through energy band theory and the electron transport mechanism. Also the ratio of D254* to D546* was calculated above 8 × 102 for all PDs, which demonstrated that our PDs showed high selectivity for detecting UV light with less influence of light with long wavelength.

The incorporation of doping elements in ZnO nanostructures plays an important role in adjusting the optical and electrical properties in optoelectronic devices. In the present study, we fabricated 1-D ZnO nanorods (NRs) doped with different In contents (0% ~ 5%) on p-GaN films using a facile hydrothermal method, and investigated the effect of the In doping on the morphology and electronic structure of the NRs and the electrical and optical performances of the n-ZnO NRs/p-GaN heterojunction light emitting diodes (LEDs). As the In content increased, the size (diameter and length) of the NRs increased, and the electrical performance of the LEDs improved. From the electroluminescence (EL) spectra, it was found that the broad green-yellow-orange emission band significantly increased with increasing In content due to the increased defect states (oxygen vacancies) in the ZnO NRs, and consequently, the superposition of the emission bands centered at 415 nm and 570 nm led to the generation of white-light. These results suggest that In doping is an effective way to tailor the morphology and the optical, electronic, and electrical properties of ZnO NRs, as well as the EL emission property of heterojunction LEDs. PMID:25988846

Metal-organic frameworks (MOFs) and related material classes are attracting considerable attention for their applications in gas storage/separation as well as catalysis. In contrast, research concerning potential uses in electronic devices (such as sensors) is in its infancy, which might be due to a great challenge in the fabrication of MOFs and semiconductor composites with well-designed structures. In this paper, we proposed a simple self-template strategy to fabricate metal oxide semiconductor@MOF core-shell heterostructures, and successfully obtained freestanding ZnO@ZIF-8 nanorods as well as vertically standing arrays (including nanorod arrays and nanotube arrays). In this synthetic process, ZnO nanorods not only act as the template but also provide Zn(2+) ions for the formation of ZIF-8. In addition, we have demonstrated that solvent composition and reaction temperature are two crucial factors for successfully fabricating well-defined ZnO@ZIF-8 heterostructures. As we expect, the as-prepared ZnO@ZIF-8 nanorod arrays display distinct photoelectrochemical response to hole scavengers with different molecule sizes (e.g., H(2)O(2) and ascorbic acid) owing to the limitation of the aperture of the ZIF-8 shell. Excitingly, such ZnO@ZIF-8 nanorod arrays were successfully applied to the detection of H(2)O(2) in the presence of serous buffer solution. Therefore, it is reasonable to believe that the semiconductor@MOFs heterostructure potentially has promising applications in many electronic devices including sensors.

Ito S. Deactivation of the TiO2 photocatalyst by coupling with WO3 and the electrochemically assisted high photocatalytic activity of WO3 . Langmuir...Synthesis of metal nanoclusters doped in porous materials as photocatalysts 5c. PROGRAM ELEMENT NUMBER 5d. PROJECT NUMBER 5d. TASK NUMBER 6...will be performed: Task #1: The development of nanoclusters embedded in zeolites as potential photocatalysts . Task #2: Identify conditions

Aluminum-doped zinc oxide (AZO) nanorod array thin film with hydrogen treatment possesses the functions of transparent conducting oxide thin film and 1-D nanostructured semiconductor simultaneously. To enhance the absorption in the visible light region, it is sensitized by cadmium sulfide (CdS) nanoparticles which efficiently increase the absorption around 460 nm. The CdS nanoparticles-sensitized AZO nanorod array thin film with hydrogen treatment exhibits significantly improved photoelectrochemical property. After further heat treatment, a maximum short current density of 5.03 mA cm−2 is obtained under illumination. They not only are much higher than those without CdS nanoparticles sensitization and those without Al-doping and/or hydrogen treatment, but also comparable and even slightly superior to some earlier works for the CdS-sensitized zinc oxide nanorod array thin films with indium tin oxide (ITO) or fluorine-doped tin oxide (FTO) as substrates. This demonstrated successfully that the AZO nanorod array thin film with hydrogen treatment is quite suitable as an ITO/FTO-free photoanode and has great potentials in solar water splitting after sensitization by quantum dots capable of visible light absorption. PMID:23098050

A highly sensitive luminescent bioassay for the detection of Salmonella typhimurium was fabricated using Mn2 +-doped NaYF4:Yb,Tm upconversion nanoparticles (UCNPs) as the donor and gold nanorods (Au NRs) as the acceptor and utilizing an energy transfer (LET) system. Mn2 +-doped NaYF4:Yb,Tm UCNPs with a strong emission peak at 807 nm were obtained by changing the doped ion ratio. Carboxyl-terminated Mn2 +-doped NaYF4:Yb,Tm UCNPs were coupled with S. typhimurium aptamers, which were employed to capture and concentrate S. typhimurium. The electrostatic interactions shorten the distance between the negatively charged donor and the positively charged acceptor, which results in luminescence quenching. The added S. typhimurium leads to the restoration of luminescence due to the formation of UCNPs-aptamers-S. typhimurium, which repels the UCNPs-aptamers from the Au NRs. The LET system does not occur because of the nonexistence of the luminescence emission band of Mn2 +-doped NaYF4:Yb,Tm UCNPs, which had large spectral overlap with the absorption band of Au NRs. Under optimal conditions, the linear range of detecting S. typhimurium was 12 to 5 × 105 cfu/mL (R = 0.99). The limit of detection for S. typhimurium was as low as 11 cfu/mL in an aqueous buffer. The measurement of S. typhimurium in milk samples was satisfied in accordance with the plate-counting method, suggesting that the proposed method was of practical value in the application of food security.

When nanorods of Au, Ag and some other elements are aligned with a preferred orientation with respect to light, their optical extinction characteristics become dependent on the polarization and angle of incidence of the light. This effect is explored here and it is shown that it could potentially be exploited to produce a 'colour-change coating'. However, particle-particle interactions are also likely to occur in such coatings, with red shifting of extinction spectra occurring for end-on-end configurations of monodisperse rods, and blue shifting for side-by-side configurations. Surprisingly, the particle-particle interactions are attenuated if they are between rods of differing aspect ratios, and this offers a useful new means of control of the optical properties of coatings of nanorods.

Biological, physical and mechanical properties of silver-doped layers of titanium alloy Ti6Al4V and 316 L steel prepared by pulsed laser deposition were studied. Metallic silver-doped coatings could be a new route for antibacterial protection in medicine. Thin films of silver and silver-doped materials were synthesized using KrF excimer laser deposition. The materials were ablated from two targets, which were composed either from titanium alloy with silver segments or from steel with silver segments. The concentration of silver ranged from 1.54 to 4.32 at% for steel and from 3.04 to 13.05 at% for titanium alloy. The layer properties such as silver content, structure, adhesion, surface wettability, and antibacterial efficiency (evaluated by Escherichia coli and Bacillus subtilis bacteria) were measured. Film adhesion was studied using a scratch test. The antibacterial efficiency changed with silver doping up to 99.9 %. Our investigation was focused on the minimum Ag concentration needed to reach high antibacterial efficiency, high film adhesion, and hardness.

We report the use of metal-semiconductor Schottky junctions in a conjugated polymer matrix as solar cells. The Schottky diodes, which were formed between Bi2S3 nanorods and gold nanoparticles, efficiently dissociated photogenerated excitons. The bulk-heterojunction (BHJ) devices based on such metal-semiconductor Schottky diodes in a polymer matrix therefore acted as an efficient solar cell as compared to the devices based on only the semiconductor nanorods in the polymer matrix or when gold nanoparticles were added separately to the BHJs. In the latter device, gold nanoparticles offered plasmonic enhancement due to an increased cross-section of optical absorption. We report growth and characteristics of the Schottky junctions formed through an intimate contact between Bi2S3 nanorods and gold nanoparticles. We also report fabrication and characterization of BHJ solar cells based on such heterojunctions. We highlight the benefit of using metal-semiconductor Schottky diodes over only inorganic semiconductor nanorods or quantum dots in a polymer matrix in forming hybrid BHJ solar cells.

We report the use of metal-semiconductor Schottky junctions in a conjugated polymer matrix as solar cells. The Schottky diodes, which were formed between Bi{sub 2}S{sub 3} nanorods and gold nanoparticles, efficiently dissociated photogenerated excitons. The bulk-heterojunction (BHJ) devices based on such metal-semiconductor Schottky diodes in a polymer matrix therefore acted as an efficient solar cell as compared to the devices based on only the semiconductor nanorods in the polymer matrix or when gold nanoparticles were added separately to the BHJs. In the latter device, gold nanoparticles offered plasmonic enhancement due to an increased cross-section of optical absorption. We report growth and characteristics of the Schottky junctions formed through an intimate contact between Bi{sub 2}S{sub 3} nanorods and gold nanoparticles. We also report fabrication and characterization of BHJ solar cells based on such heterojunctions. We highlight the benefit of using metal-semiconductor Schottky diodes over only inorganic semiconductor nanorods or quantum dots in a polymer matrix in forming hybrid BHJ solar cells.

Nitrogen-doped (N-doped) single-wall carbon nanotubes (SWCNTs) were synthesized by chemical vapor deposition using SiOx nanoparticles as a catalyst and ethylenediamine as the source of both carbon and nitrogen. The N-doped SWCNTs have a mean diameter of 1.1 nm and a narrow diameter range, with 92% of them having diameters from 0.7 to 1.4 nm. Multi-wavelength laser Raman spectra and temperature-dependent electrical resistance indicate that the SWCNT sample is enriched with metallic nanotubes. These N-doped SWCNTs showed excellent electrocatalytic activity for the oxygen reduction reaction and highly selective and sensitive sensing ability for dopamine detection.

We investigate the geometric structure and electronic and magnetic properties of 3d-transition-metal atom doped antimonene using spin-polarized first-principles calculations. Strong orbital hybridization exhibits between 3d-transition-metal and Sb atoms, where covalent bonds form in antimonene. A spin-polarized semiconducting state appears in Cr-doped antimonene, while half-metallic states appear by doping Ti, V, and Mn. These findings indicate that once combined with doping states, the bands of antimonene systems offer a variety of features. Specific dopants lead to half-metallic characters with high spin polarization that has potential application in spintronics.

Nitrogen-doped (N-doped) single-wall carbon nanotubes (SWCNTs) were synthesized by chemical vapor deposition using SiOx nanoparticles as a catalyst and ethylenediamine as the source of both carbon and nitrogen. The N-doped SWCNTs have a mean diameter of 1.1 nm and a narrow diameter range, with 92% of them having diameters from 0.7 to 1.4 nm. Multi-wavelength laser Raman spectra and temperature-dependent electrical resistance indicate that the SWCNT sample is enriched with metallic nanotubes. These N-doped SWCNTs showed excellent electrocatalytic activity for the oxygen reduction reaction and highly selective and sensitive sensing ability for dopamine detection.Nitrogen-doped (N-doped) single-wall carbon nanotubes (SWCNTs) were synthesized by chemical vapor deposition using SiOx nanoparticles as a catalyst and ethylenediamine as the source of both carbon and nitrogen. The N-doped SWCNTs have a mean diameter of 1.1 nm and a narrow diameter range, with 92% of them having diameters from 0.7 to 1.4 nm. Multi-wavelength laser Raman spectra and temperature-dependent electrical resistance indicate that the SWCNT sample is enriched with metallic nanotubes. These N-doped SWCNTs showed excellent electrocatalytic activity for the oxygen reduction reaction and highly selective and sensitive sensing ability for dopamine detection. Electronic supplementary information (ESI) available: Additional information including Raman spectra, ORR polarization curves, CV curves, etc. See DOI: 10.1039/c4nr03172e

ZnO(Fe)/ZnO multilayers (MLs) with Fe 6.5% (Fe-doped sample) and ZnO(FeNi)/ZnO MLs with Fe22Ni78 6.5% (Ni-doped sample) prepared by helicon plasma sputtering were investigated. Structures of as-prepared Fe- and Ni-doped samples show the layer structures and the ZnO crystalline structures. However, the samples annealed at 773 K induced the formation of ZnFe2O4 for Fe doped sample, and the growth of metallic Ni for Ni-doped sample. Furthermore, Fe atoms in the annealed Fe-doped sample are dispersed mainly in the surface region, and Ni atoms in as-prepared and annealed Ni-doped samples are located uniformly in the film. The ionic states of Fe in Fe-doped sample and Ni in Ni-doped sample before and after annealing are the mixed Fe2+/3+ and metallic Ni, respectively. Therefore, it is considered that the as-prepared and the annealed Ni-doped samples form Ni particles. As-prepared samples showed the paramagnetic properties. However, the magnetic state of the as-prepared Ni-doped sample is partly superparamagnetic due to the existence of small Ni particles. On the other hand, annealed samples show the ferromagnetic characteristics due to formation of ZnFe2O4 for Fe-doped ones and growing metallic Ni particles for Ni-doped ones.

Considerable recent attention has been paid to homogeneous fluorescent DNA detection with the use of nanostructures as a universal "quencher", but it still remains a great challenge to develop such nanosensor with the benefits of low cost, high speed, sensitivity, and selectivity. In this work, we report the use of iron-based metal-organic framework nanorods as a high-efficient sensing platform for fluorescent DNA detection. It only takes about 4 min to complete the whole "mix-and-detect" process with a low detection limit of 10 pM and a strong discrimination of single point mutation. Control experiments reveal the remarkable sensing behavior is a consequence of the synergies of the metal center and organic linker. This work elucidates how composition control of nanostructures can significantly impact their sensing properties, enabling new opportunities for the rational design of functional materials for analytical applications.

In this paper, a new Bi2O3 based photocatalyst doped with varying concentration of Nb and Mn metal ion was fabricated by conventional heat treatment method and their photocatalytic activity was investigated. The prepared material was characterized by X-ray diffraction (XRD), UV-Visible Spectroscopy, Fourier transform infrared (FTIR) and Scanning Electron Microscopic (SEM) techniques. The XRD analysis of synthesized photocatalyst was found to exhibit characteristic peaks of well crystallized monoclinic α-Bi2O3. The XRD pattern of pure and metaldoped Bi2O3 were found to more or less similar. The crystallite size of doped materials were smaller than pure Bi2O3 and size decreases with increasing dopant concentration from 0.5 to 2.0% for Nb & 1.0-3.0% for Mn and remains almost constant at higher dopant concentration. The SEM analysis clearly indicate the formation of nanorod like morphologies. The UV-Vis absorption spectra of synthesized nanorods revealed that the absorption edge shift towards longer wavelength on doping with Nb and Mn metal ions which is beneficial for absorbing more visible light in the solar spectrum. The prepared doped Bi2O3 nanorod showed the excellent photocatalytic activity for degradation of selected organic pollutants, such as Methylene Blue (MB) and Rodaamime B (RhB) under visible light source. The higher activity of doped Bi2O3 nanorod may be attributed to absorption of more visible light leading to generation of higher photogenerated electron hole pairs and efficient separation of photoinduced charge carrier to inhibit the recombination rate.

We have investigated the dispersion renormalization Zdisp in La2-xSrxCuO4 over the wide doping range of x=0.03-0.30 , for binding energies extending to several hundred meV’s. Strong correlation effects conspire in such a way that the system exhibits a local-density-approximation-like dispersion which essentially “undresses” (Zdisp→1) as the Mott insulator is approached. Our finding that the Mott insulator contains “nascent” or “preformed” metallic states with a vanishing spectral weight offers a challenge to existing theoretical scenarios for cuprates.

The oxygen reduction reaction (ORR) is of high industrial importance. There is a large body of literature showing that metal-based catalytic nanoparticles (e.g. Co, Mn, Fe or hybrid Mn/Co-based nanoparticles) supported on graphene act as efficient catalysts for the ORR. A significant research effort is also directed to the so-called “metal-free” oxygen reduction reaction on heteroatom-doped graphene surfaces. While such studies of the ORR on nonmetallic heteroatom-doped graphene are advertised as “metal-free” there is typically no sufficient effort to characterize the doped materials to verify that they are indeed free of any trace metal. Here we argue that the claimed “metal-free” electrocatalysis of the oxygen reduction reaction on heteroatom-doped graphene is caused by metallic impurities present within the graphene materials.

Metal-doped single-walled carbon nanotubes and production thereof. The metal-doped single-walled carbon nanotubes may be produced according to one embodiment of the invention by combining single-walled carbon nanotube precursor material and metal in a solution, and mixing the solution to incorporate at least a portion of the metal with the single-walled carbon nanotube precursor material. Other embodiments may comprise sputter deposition, evaporation, and other mixing techniques.

The transition metal (TM) doped zinc blende boron nitride (c-BN) is studied by using the first principle calculation. TM atoms fill in the interstitials in c-BN and form two-dimensional honeycomb lattice. The generalized gradient approximation and projector augmented wave method are used. The calculated density of states and band structures show that d electrons of TM atoms form impurity bands in the gap of c-BN. When the TM-BN system is in ferromagnetic or non-magnetic state, Dirac cones emerge at the K point in Brillouin zone. When TM is Ti and Co, the Dirac cones are spin polarized and very close to the Fermi level, which makes them promising candidates of Dirac half-metal [H. Ishizuka and Y. Motome, Phys. Rev. Lett. 109, 237207 (2012)]. While TM is Ni and Cu, the system is non-magnetic and Dirac cones located above the Fermi level.

Bifunctional hexagonal Tm(3+) doped NaYb0.55Gd0.45F4 nanorods with tunable size are prepared via in situ cation-exchange reaction using hydrothermal method. The measured field dependence of magnetization of the NaYb0.55Gd0.45F4 nanorods shows typical paramagnetic characteristics that can be ascribed to the non-interacting localized nature of the magnetic moment of rare-earth ions. When excited by a 980nm laser, these nanorods exhibit intense multi-color up-conversion (UC) emissions in infrared, red, blue and especially ultraviolet. In addition, luminescent switching between different UC emission wavelengths of 480nm and 450nm is observed by adjusting Tm(3+) doping concentration. Based on power-dependent spectral analyses, it is found that with the increase of Tm(3+) doping concentration, due to the suppressed saturation effect, the dominative UC process redistribute the populations at (1)G4 and (1)D2(Tm(3+)) states of Tm(3+) ion resulting in the above luminescent switching. Our results indicate that bifunctional hexagonal NaYb1-xGdxF4 nanocrystals have potential applications in miniaturized solid-state light sources, optical processing sensors and fluorescent biolabels.

Bifunctional hexagonal Tm3+ doped NaYb0.55Gd0.45F4 nanorods with tunable size are prepared via in situ cation-exchange reaction using hydrothermal method. The measured field dependence of magnetization of the NaYb0.55Gd0.45F4 nanorods shows typical paramagnetic characteristics that can be ascribed to the non-interacting localized nature of the magnetic moment of rare-earth ions. When excited by a 980 nm laser, these nanorods exhibit intense multi-color up-conversion (UC) emissions in infrared, red, blue and especially ultraviolet. In addition, luminescent switching between different UC emission wavelengths of 480 nm and 450 nm is observed by adjusting Tm3+ doping concentration. Based on power-dependent spectral analyses, it is found that with the increase of Tm3+ doping concentration, due to the suppressed saturation effect, the dominative UC process redistribute the populations at 1G4 and 1D2(Tm3+) states of Tm3+ ion resulting in the above luminescent switching. Our results indicate that bifunctional hexagonal NaYb1-xGdxF4 nanocrystals have potential applications in miniaturized solid-state light sources, optical processing sensors and fluorescent biolabels.

Metal Fe or Cu doped P25 titania was prepared using the photodeposition method and characterized by TEM, ICP, XRD and UV-Vis, further tested for photocatalytic nitrate reduction and TN removal, under 20 W UV lamp irradiation. The influencing factors such as the pH values of solution, stirring gas, metal loadings, hole scavenger formic acid amount and co-doped Ag-Cu/TiO2 are investigated and discussed in detail. The experimental results after 2 h reaction indicated that with the increase of Cu loadings, nitrate conversion increases too, while a loading of 0.5% is optimal for highest N2 selectivity and TN (total nitrogen) removal. Using N2 as stirring gas and under acidic conditions, the N2 selectivity is lower (62%), but the highest conversion of nitrate and removal of TN can reach 36.9% and 23.2% respectively. Using CO2 as stirring gas, the highest selectivity for nitrogen 88.4% is obtained with 0.5% Cu/TiO2, 0.06 mol/L formic acid. Under the same conditions, using the prepared bimetallic titania (1%, 1:1 Ag/Cu), the conversion of nitrate and removal of TN are 48.1%, 34.2%, and N2 selectivity is 72.2%.

Highlights: • Polar and semipolar ZnO NRs were successfully achieved by hydrothermal synthesis. • Semipolar and polar ZnO NRs were grown on ZnO and AZO/m-sapphire, respectively. • Al % of AZO/m-sapphire enhanced the lateral growth rate of polar ZnO NRs. - Abstract: We investigated the effect of an Al-doped ZnO film on the crystallographic direction of ZnO nanorods (NRs) using electrochemical deposition. From high-solution X-ray diffraction measurements, the crystallographic plane of ZnO NRs grown on (1 0 0) ZnO/m-plane sapphire was (1 0 1). The surface grain size of the (100) Al-doped ZnO (AZO) film decreased with increasing Al content in the ZnO seed layer, implying that the Al dopant accelerated the three-dimensional (3D) growth of the AZO film. In addition, it was found that with increasing Al doping concentration of the AZO seed layer, the crystal orientation of the ZnO NRs grown on the AZO seed layer changed from [1 0 1] to [0 0 1]. With increasing Al content of the nonpolar (1 0 0) AZO seed layer, the small surface grains with a few crystallographic planes of the AZO film changed from semipolar (1 0 1) ZnO NRs to polar (0 0 1) ZnO NRs due to the increase of the vertical [0 0 1] growth rate of the ZnO NRs owing to excellent electrical properties.

The pure face-centered-cubic PbTe nanorods have been synthesized by the composite-hydroxide-mediated approach using hydrazine as a reducing agent. The method is based on reaction among reactants in the melts of potassium hydroxide and sodium hydroxide eutectic at 170-220 deg. C and normal atmosphere without using any organic dispersant or surface-capping agent. Scanning electron microscopy, X-ray diffraction, transmission electron microscopy, and energy dispersive X-ray spectroscopy were used to characterize the structure, morphology and composition of the samples. The diameters of nanorods are almost fixed, while the lengths can be tunable under different growth time and temperatures. The growth mechanism of PbTe nanorods is investigated via UV-vis absorption, demonstrating that polymerized tellurium anions and metal(II) amides in the hydrazine hydroxide melts could control the crystallization and growth process of PbTe nanostructures. The band gap of as-synthesized PbTe nanorods has been calculated based on UV-vis-NIR optical diffuse reflectance spectra data.

Vertically aligned ZnO nanorod arrays have been synthesized on c-plane sapphires at a low temperature of 400 degrees C using catalyst-free inductively coupled plasma (ICP) metal organic chemical vapor deposition (MOCVD) technique by varying the ICP powers. Diameters of the ZnO nanorods changed from 200 nm to 400 nm as the ICP power increased from 200 to 400 Watt. TEM and XRD investigations indicated that the ZnO nanorod arrays grown at ICP powers above 200 Watt had a homogeneous in-plane alignment and single crystalline nature. PL study at room temperature (RT) and 6 K confirmed that the ZnO nanorod arrays in the present study are of high optical quality as well as good crystalline quality, showing only exciton-related emission peaks without any trace of defect-related deep level emissions in visible range. The blueshift of exciton emission peak in RTPL spectra was also found as rod diameter decreased and it is deduced that this shift in emission energy may be due to the surface resonance effect resulted from the increased surface-to-volume ratio, based on the observation and behavior of the surface exciton (SX) emission in the high-resolution 6 K PL spectra.

Silver nanorods (AgNRs) with lengths in the 50-60 nm range were synthesized and functionalized with 2-(2-mercaptoethyl)thioxanthone (C2TX) to generate AgNR@C2TX nanoassemblies. When irradiated at 377 nm in the presence of a diacrylate monomer, these dispersed nanoassemblies initiate radical photopolymerization, indicating that the excited singlet to triplet intersystem crossing process of C2TX in the vicinity of AgNRs was favored while the fluorescence of C2TX was completely quenched at the surface of NRs. SEM and TEM images confirmed the formation of a AgNR-polymer nanocomposite and the homogeneous dispersion of AgNRs in the polymer film. Moreover, under specific experimental conditions allowing the spatial extent of the polymerization to be limited, polymer-capped AgNRs were obtained (polymer diameter of ca. 1 nm).Silver nanorods (AgNRs) with lengths in the 50-60 nm range were synthesized and functionalized with 2-(2-mercaptoethyl)thioxanthone (C2TX) to generate AgNR@C2TX nanoassemblies. When irradiated at 377 nm in the presence of a diacrylate monomer, these dispersed nanoassemblies initiate radical photopolymerization, indicating that the excited singlet to triplet intersystem crossing process of C2TX in the vicinity of AgNRs was favored while the fluorescence of C2TX was completely quenched at the surface of NRs. SEM and TEM images confirmed the formation of a AgNR-polymer nanocomposite and the homogeneous dispersion of AgNRs in the polymer film. Moreover, under specific experimental conditions allowing the spatial extent of the polymerization to be limited, polymer-capped AgNRs were obtained (polymer diameter of ca. 1 nm). Electronic supplementary information (ESI) available: Additional TEM image. See DOI: 10.1039/c3nr01256e

It is possible to stabilize CrO2 internally by doping with element such as Ti, Sn or Ru which has stable rutile structured oxide. However, the half metallicity and magnetic properties of CrO2 may also change when doped with different elements. In this study, by using first principle method, the electronic structure and magnetic properties of CrO2 doped with different amounts and different types (Ti, Sn or Ru) of dopants were studied. It was found that when doped with Ti or Sn, the half metallicity of CrO2 will keep intact even at very high dopant concentration, while for Ru-doped CrO2, the half metallicity will only be maintained at low Ru concentration. Besides, the half metallicity of Ru-doped CrO2 also depends on the relative positions of Ru atoms - the half metallicity may be destroyed even at low Ru concentration if two Ru ions are very close to each other. The magnetic properties of doped CrO2 also show dependence on dopant concentration and dopant type. The magnetocrystalline anisotropy (MAC) of Ru-doped is found to be very sensitive to both Ru concentration and relative positions of Ru atoms. Large MAC may be induced by Ru doping.

Here, we propose a novel DNA-based doping method on MoS2 and WSe2 films, which enables ultra-low n- and p-doping control and allows for proper adjustments in device performance. This is achieved by selecting and/or combining different types of divalent metal and trivalent lanthanide (Ln) ions on DNA nanostructures, using the newly proposed concept of Co-DNA (DNA functionalized by both divalent metal and trivalent Ln ions). The available n-doping range on the MoS2 by Ln-DNA is between 6 × 109 and 2.6 × 1010 cm−2. The p-doping change on WSe2 by Ln-DNA is adjusted between −1.0 × 1010 and −2.4 × 1010 cm−2. In Eu3+ or Gd3+-Co-DNA doping, a light p-doping is observed on MoS2 and WSe2 (~1010 cm−2). However, in the devices doped by Tb3+ or Er3+-Co-DNA, a light n-doping (~1010 cm−2) occurs. A significant increase in on-current is also observed on the MoS2 and WSe2 devices, which are, respectively, doped by Tb3+- and Gd3+-Co-DNA, due to the reduction of effective barrier heights by the doping. In terms of optoelectronic device performance, the Tb3+ or Er3+-Co-DNA (n-doping) and the Eu3+ or Gd3+-Co-DNA (p-doping) improve the MoS2 and WSe2 photodetectors, respectively. We also show an excellent absorbing property by Tb3+ ions on the TMD photodetectors. PMID:26838524

Dye sensitized solar cell (DSSC) using ZnO nanoparticles provides a technically and economically credible alternative concept to present day p-n junction photovoltic device. The conventional systems where the semiconductors assume both the task of light absorption and charge carrier transport the two junctions are seprated here. In DSSC the light is absorbed by a sensitizer. In our investigation the DSSC consist of Zno nanoparticles that have a large surface area are used to harvest sunlight. Firstly the ZnO nanoparticals were grown on FTO substrate and then this nanoparticals were used as seed layers to grow aligned nanorods and used them as the wide band gap semiconductor electrod for solar cell. ZnO electrodes were sensitized by Rhodamine 6G dye. ZnO nanoparticles and nanorods were observed through SEM and their crystallinity were investigated using XRD. The higher efficiency in DSSC is possible due to the increased surface area from the nanoparticles facilitating the fast electron transport through the nanowires.

TiO2 nanorods were successfully grown on Tantalum (Ta) substrates using titanium tetra isopropoxide (TTIP) as a single precursor without any carriers or bubbling gases. For characterization of the TiO2 structures, scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) were employed. For substrate temperatures below 800 degrees C, a rough film structure without nanorods could be found. However, at a sample temperature of 800 degrees C, nanorod structures with a respective diameter and length of 0.1 approximately 0.2 microm and 0.7 approximately 1.5 microm, respectively, could be synthesized. The nanorods exhibited a rutile phase with a 2:1 stoichiometry of O:Ti, identified using XRD and XPS. When the growth temperature exceeded 800 degrees C, agglomeration of the nanorods was identified.

Catalytic oxidation of carbon monoxide (CO) is of great importance in many different fields of industry. Until now it still remains challenging to use non-noble metal based catalysts to oxidize CO at low temperature. Herein, we report a new class of nanoporous, uniform, and transition metal-doped cerium (IV) oxide (ceria, CeO2) microsphere for CO oxidation catalysis. The porous and uniform microsphere is generated by sacrificed polymer template. Transition-metals, like Cu, Co, Ni, Mn and Fe, were doped into CeO2 microspheres. The combination of hierarchical structure and metaldoping afford superior catalytic activities of the doped ceria microspheres, which could pave a new way to advanced non-precious metal based catalysts for CO oxidation. PMID:27030159

Catalytic oxidation of carbon monoxide (CO) is of great importance in many different fields of industry. Until now it still remains challenging to use non-noble metal based catalysts to oxidize CO at low temperature. Herein, we report a new class of nanoporous, uniform, and transition metal-doped cerium (IV) oxide (ceria, CeO2) microsphere for CO oxidation catalysis. The porous and uniform microsphere is generated by sacrificed polymer template. Transition-metals, like Cu, Co, Ni, Mn and Fe, were doped into CeO2 microspheres. The combination of hierarchical structure and metaldoping afford superior catalytic activities of the doped ceria microspheres, which could pave a new way to advanced non-precious metal based catalysts for CO oxidation.

We demonstrate in a simple model the surprising result that turning on an on-site Coulomb interaction U in a doped band insulator leads to the formation of a half-metallic state. In the undoped system, we show that increasing U leads to a first order transition at a finite value UAF between a paramagnetic band insulator and an antiferomagnetic Mott insulator. Upon doping, the system exhibits half-metallic ferrimagnetism over a wide range of doping and interaction strengths on either side of UAF. Our results, based on dynamical mean field theory, suggest a new route to half metallicity, and will hopefully motivate searches for new materials for spintronics.

Various metal-doped p-type CaFe2O4 photocathodes were prepared in an attempt to improve the low quantum efficiency for photoreaction. CuO and Au doping enhanced the photocurrent by expansion of the absorption wavelength region and plasmon resonance, respectively. X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS) analysis showed that doping with these metals further disturbed the originally distorted crystal structure of CaFe2O4. In contrast, doping with Ag relaxed the distorted crystal structure around the Fe center toward symmetry. Ag doping resulted in improvement of the carrier mobility together with a red-shift of photoabsorption with Ag-doped CaFe2O4 having a 23-fold higher photocurrent than undoped CaFe2O4.

In this paper, we have synthesized Zn{sub 1−x}Ag{sub x}O (x = 0, 0.03, 0.06, and 0.09) nanorods (NRs) via the hydrothermal method at low temperature on silicon substrate. The characterization and comparison between the different Zn{sub 1−x}Ag{sub x}O samples, indicated that an increasing Ag concentration from x = 0 to a maximum of x = 0.09; All samples show a preferred orientation of (002) direction with no observable change of morphology. As the quantity of the Ag dopant was changed, the transmittances, as well as the optical band gap were decreased. X-ray photoelectron spectroscopy data clearly indicate the presence of Ag in ZnO crystal lattice. A nanoindentation-based technique was used to measure the effective piezo-response of different concentrations of Ag for both direct and converse effects. The value of the piezoelectric coefficient (d{sub 33}) as well as the piezo potential generated from the ZnO NRs and Zn{sub 1−x}Ag{sub x}O NRs was found to decrease with the increase of Ag fraction. The finding in this investigation reveals that Ag doped ZnO is not suitable for piezoelectric energy harvesting devices.

In this paper, we have synthesized Zn1-xAgxO (x = 0, 0.03, 0.06, and 0.09) nanorods (NRs) via the hydrothermal method at low temperature on silicon substrate. The characterization and comparison between the different Zn1-xAgxO samples, indicated that an increasing Ag concentration from x = 0 to a maximum of x = 0.09; All samples show a preferred orientation of (002) direction with no observable change of morphology. As the quantity of the Ag dopant was changed, the transmittances, as well as the optical band gap were decreased. X-ray photoelectron spectroscopy data clearly indicate the presence of Ag in ZnO crystal lattice. A nanoindentation-based technique was used to measure the effective piezo-response of different concentrations of Ag for both direct and converse effects. The value of the piezoelectric coefficient (d33) as well as the piezo potential generated from the ZnO NRs and Zn1-xAgxO NRs was found to decrease with the increase of Ag fraction. The finding in this investigation reveals that Ag doped ZnO is not suitable for piezoelectric energy harvesting devices.

Perovskite LaMnO3 nanorod/reduced graphene oxides (LMO-NR/RGO) decorated with Ag nanoparticles are studied as a bifunctional catalyst for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline electrolyte. LMO-NR/RGO composites are synthesized by using cetyltrimethyl ammonium bromide (CTAB) as template via a simple hydrothermal reaction followed by heat treatment; overlaying of Ag nanoparticles is obtained through a traditional silver mirror reaction. Electron microscopy reveals that LMO-NR is embedded between the sheets of RGO, and the material is homogeneously overlaid with Ag nanoparticles. The unique composite morphology of Ag/LMO-NR/RGO not only enhances the electron transport property by increasing conductivity but also facilitates the diffusion of electrolytes and oxygen. As confirmed by electrochemical testing, Ag/LMO-NR/RGO exhibits very strong synergy with Ag nanoparticles, LMO-NR, and RGO, and the catalytic activities of Ag/LMO-NR/RGO during ORR and OER are significantly improved. With the novel catalyst, the homemade zinc-air battery can be reversibly charged and discharged and display a stable cycle performance, indicating the great potential of this composite as an efficient bifunctional electrocatalyst for metal-air batteries.

We have demonstrated that the island nucleation in the initial stage of epitaxial thin film growth can be tuned by substrate surface charge doping. This charge effect was investigated using spin density functional theory calculation in Fe-deposition on graphene substrate as an example. It was found that hole-doping can noticeably increase both Fe-adatom diffusion barrier and Fe inter-adatom repulsion energy occurring at intermediate separation, whereas electron-doping can decrease Fe-adatom diffusion barrier but only slightly modify inter-adatom repulsion energy. Further kinetic Monte Carlo simulation showed that the nucleation island number density can be increased up to six times larger under hole-doping and can be decreased down to ten times smaller under electron doping than that without doping. Our findings indicate a route to tailor the growth morphology of magnetic metal nanostructure for spintronics and plasmonic applications via surface charge doping.

A laser direct write and doping (LDWD) system is designed and utilized for direct metallization and selective area doping in different SiC polytypes, GaN and in dielectrics including AlN. Laser direct metallization in 4H- and 6H-SiC generates metal-like conductive phases that are produced as both rectifying and ohmic contacts without metal deposition. Nd:YAG (lambda = 532, 1064 nm) nanosecond pulsed laser irradiation in SiC induces carbon-rich conductive phases by thermal decomposition of SiC while UV excimer (lambda = 193 nm) laser irradiation produces a silicon-rich phase due to selective carbon photoablation. Linear transmission line method (TLM) pattern is directly fabricated in single crystals SiC by pulsed laser irradiation allowing characterization of the laser fabricated metal-like contacts. Activation of a self focusing effect at the frequency doubled Nd:YAG laser irradiation (lambda = 532 nm) allows to fabricate buried metal like contacts in SiC wafers while maintaining their device-ready surface condition. Gas immersion laser doping (GILD) and laser doping from a molten precursor are utilized to dope both GaN and SiC. Trimethylaluminum (TMAl) and nitrogen are the precursors used to produce p-type and n-type doped SiC; respectively. Nd:YAG and excimer laser nitrogen doping in SiC epilayer and single crystal substrates increases the dopant concentration by two orders of magnitude and produces both deep (500--600 nm) and shallow (50 nm) junctions, respectively. Laser assisted effusion/diffusion is introduced and utilized to dope Al in SiC wafers. Using this technique, a150 nm p-type doped junction is fabricated in semi-insulating 6H- and n-type doped 4H-SiC wafers. Laser-induced p-type doping of Mg in single crystal GaN is conducted using Bis-magnesium dihydrate [Mg(TMHD)2]. Mg concentration and penetration depth up to 10 20--1021 cm-3 and 5mum, respectively are achieved using various laser doping techniques. Laser direct writing and doping (LDWD) is a

Optical antenna can strongly enhance the interaction of light with matter by their ability to localize electromagnetic fields on nano-metric scale. This allows for the engineering of absorption capabilities to visible and infrared detectors with very small active areas. In this study, we focused on the study of metal and semiconductor infrared antennas for nano-bolometer application. The infrared antennas are applied for increasing the effective absorbing across section, enhancing the field intensity at the gap of the antennas and improving the absorbance of bolometer materials located at the gap. We perform numerical simulation of the characteristics of infrared antennas and analysis the influence of various parameters of antennas (length, wide, and material types) and optimized these parameters to achieve the maximum field enhancement for an optical antenna. We also highlight the comparisons of field enhancement of infrared antenna materials between metal and highly doped semiconductor and discuss some practical issues related to the application of infrared antenna for infrared detectors.

Various kinds of metal (Co, Pd, Pt and Au) were doped into Ag2O and AgO sputtered films to study its effect on the thermal decomposition process. The oxygen composition ratio was evaluated by the X-ray fluorescence spectroscopy method after annealing up to 260,oC. The optical transmittance change was measured during heating of the film to 600,oC. Noble metaldoping was found to modify the AgO decomposition process, and the oxygen content decreased gradually compared to the undoped case. Super-RENS disks with a metal-doped AgO mask were prepared, and the laser power necessary for super-resolutional readout was evaluated. It slightly shifted to the higher-power side when the noble metal was doped, and this agrees with the modification of the decomposition process.Japan Science and Technology Corporation, Domestic Research Fellow

Metal decorated graphene materials are highly important for catalysis. In this work, noble metaldoped-graphene hybrids were prepared by a simple and scalable method. The thermal reductions of metaldoped-graphite oxide precursors were carried out in nitrogen and hydrogen atmospheres and the effects of these atmospheres as well as the metal components on the characteristics and catalytic capabilities of the hybrid materials were studied. The hybrids exfoliated in nitrogen atmosphere contained a higher amount of oxygen-containing groups and lower density of defects on their surfaces than hybrids exfoliated in hydrogen atmosphere. The metals significantly affected the electrochemical behavior and catalysis of compounds that are important in energy production and storage and in electrochemical sensing. Research in the field of energy storage and production, electrochemical sensing and biosensing as well as biomedical devices can take advantage of the properties and catalytic capabilities of the metaldoped graphene hybrids.

Spurred by the decreased availability of fossil fuels and global warming, the idea of converting solar energy into clean fuels has been widely recognized. Hydrogen produced by photoelectrochemical water splitting using sunlight could provide a carbon dioxide lean fuel as an alternative to fossil fuels. A major challenge in photoelectrochemical water splitting is to develop an efficient photoanode that can stably oxidize water into oxygen. Here we report an efficient and stable photoanode that couples an active barium-doped tantalum nitride nanostructure with a stable cobalt phosphate co-catalyst. The effect of barium doping on the photoelectrochemical activity of the photoanode is investigated. The photoanode yields a maximum solar energy conversion efficiency of 1.5%, which is more than three times higher than that of state-of-the-art single-photon photoanodes. Further, stoichiometric oxygen and hydrogen are stably produced on the photoanode and the counter electrode with Faraday efficiency of almost unity for 100 min.

An attempt has been made to realize p-type ZnO by dual acceptor doping (Na-N) into ZnO thin films. Na and N doped ZnO thin films of different concentrations (0 to 8 at.%) have been grown by spray pyrolysis at 623 K. The grown films on glass substrate have been characterized by X-ray diffraction (XRD), Hall measurement, UV-Vis spectrophotometer, Photoluminescence (PL) and Energy dispersive spectroscopy (EDS) to validate the p-type conduction. The surface morphology and roughness of the ZnO:(Na, N) films are studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM), respectively. Hall measurement shows that all the films exhibit p-type conductivity except for 0 at.% Na-N doped ZnO film. The obtained resistivity (5.60×10{sup −2} Ω cm) and hole concentration (3.15×10{sup 18} cm{sup −3}) for the best dual acceptor doped film is 6 at.%. It has been predicted that (Na{sub Zn}−N{sub O}) acceptor complex is responsible for the p-type conduction. The p-type conductivity of the ZnO:(Na, N) films is stable even after 6 months. The crystallinity of the films has been studied by XRD. Energy dispersive spectroscopy (EDS) confirms the presence of Na and N in 6 at.% ZnO:(Na, N) film. Photoluminescence (PL) spectra of ZnO:(Na, N) films show NBE and deep level emissions in the UV and visible regions, respectively. The ZnO:(Na, N) films exhibit a high transmittance about 90% in the visible region.

ZnS and transition metal (Mn, Co, Ni, Cu, Ag and Cd) doped ZnS were synthesized using chemical precipitation method in an air atmosphere. The structural and optical properties were studied using various techniques. The X-ray diffraction (XRD) analysis show that the particles are in cubic structure. The mean size of the nanoparticles calculated through Scherrer equation is in the range of 4-6.1 nm. Elemental dispersive (EDX) analysis of doped samples reveals the presence of doping ions. The scanning electron microscopic (SEM) and transmission electron microscopic (TEM) studies show that the synthesized particles are in spherical shape. Optical characterization of both undoped and doped samples was carried out by ultraviolet-visible (UV-Vis) and photoluminescence (PL) spectroscopy. The absorption spectra of all the samples are blue shifted from the bulk ZnS. An optimum doping level of the transition metals for enhanced PL properties are found through optical study.

The emergence of metallic conduction in layered dichalcogenide semiconductor materials by chemical doping is one of key issues for two-dimensional (2D) materials engineering. At present, doping methods for layered dichalcogenide materials have been limited to an ion intercalation between layer units or electrostatic carrier doping by electrical bias owing to the absence of appropriate substitutional dopant for increasing the carrier concentration. Here, we report the occurrence of metallic conduction in the layered dichalcogenide of SnSe2 by the direct Se-site doping with Cl as a shallow electron donor. The total carrier concentration up to ~1020 cm−3 is achieved by Cl substitutional doping, resulting in the improved conductivity value of ~170 S·cm−1 from ~1.7 S·cm−1 for non-doped SnSe2. When the carrier concentration exceeds ~1019 cm−3, the conduction mechanism is changed from hopping to degenerate conduction, exhibiting metal-insulator transition behavior. Detailed band structure calculation reveals that the hybridized s-p orbital from Sn 5s and Se 4p states is responsible for the degenerate metallic conduction in electron-doped SnSe2. PMID:26792630

The development of electrocatalysts is crucial for renewable energy applications. Metal-doped graphene hybrid materials have been explored for this purpose, however, with much focus on noble metals, which are limited by their low availability and high costs. Transition metals may serve as promising alternatives. Here, transition metal-doped graphene hybrids were synthesized by a simple and scalable method. Metal-doped graphite oxide precursors were thermally exfoliated in either hydrogen or nitrogen atmosphere; by changing exfoliation atmospheres from inert to reductive, we produced materials with different degrees of oxidation. Effects of the presence of metal nanoparticles and exfoliation atmosphere on the morphology and electrocatalytic activity of the hybrid materials were investigated using electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and cyclic voltammetry. Doping of graphene with transition metal nanoparticles of the 4th period significantly influenced the electrocatalysis of compounds important in energy production and storage applications, with hybrid materials exfoliated in nitrogen atmosphere displaying superior performance over those exfoliated in hydrogen atmosphere. Moreover, nickel-doped graphene hybrids displayed outstanding electrocatalytic activities towards reduction of O2 when compared to bare graphenes. These findings may be exploited in the research field of renewable energy.

The effect of co-doping with transition metals (Fe, Ni, and Sm) on the thermoelectric properties of Al-doped ZnO (AZO) ceramics was studied. The electrical conductivity σ of AZO was significantly (12%) increased by Ni co-doping, while an unfavorable deterioration in σ was observed for Fe- or Sm-co-doped AZO. Hall-effect measurements indicated that the electron mobility of AZO decreased due to co-doping in all samples. Only the Ni-co-doped AZO sample showed significant enhancement in electron density, resulting in its black color. The thermal conductivity κ decreased drastically due to Ni or Sm co-doping of AZO, while only a small change was observed for Fe co-doping of AZO. The κ value at 1073 K for Ni-co-doped AZO was 77% of that for AZO. A dimensionless figure of merit ZT = 0.126 was attained at 1073 K for Ni-co-doped AZO, representing an improvement over that of conventional AZO by a factor of 1.50.

We report an electrochemical synthesis of homogeneous and well-aligned ZnO nanorods (NRs) on transparent conducting aluminium-doped zinc oxide (AZO) thin films as electrodes. The selected ZnO NRs was then chemically corroded in HCl and KCl aqueous solutions to form nanopencils (NPs), and nanotubes (NTs), respectively. A DC magnetron sputtering was employed to fabricate AZO thin films at various thicknesses. The obtained AZO thin films have a c-direction orientation, transmittance above 80% in visible region, and sheet resistance approximately 40 Ω/sq. They are considered to be relevant as electrodes and seeding layers for electrochemical. The ZnO NRs are directly grown on the AZOs without a need of catalysts or additional seeding layers at temperature as low as 85 degrees C. Their shapes are strongly associated with the AZO thickness that provides a valuable way to control the diameter of ZnO NRs grown atop. With the addition of HCI and KCl aqueous solutions, ZnO NRs were modified their shape to NPs and NTs with the reaction time, respectively. All the ZnO NRs, NPs, and NTs are preferred to grow along c-direction that indicates a lattice matching between AZO thin films and ZnO nanostructrures. Photoluminescence spectra and XRD patterns show that they have good crystallinities. A great photocatalytic activity of ZnO nanostructures promises potential application in environmental treatment and protection. The ZnO NTs exhibits a higher photocatalysis than others possibly due to the oxygen vacancies on the surface and the polarizability of Zn2+ and O2-.

Using first-principles calculations, we studied the magnetic properties of 3d transition-metal (TM) atoms doped phosphorene. The magnetic moments are 1.02, 2.00, 3.00, 4.04, 1.01 and 0.93 μB for Ti, V, Cr, Mn, Fe and Ni doped phosphorene, respectively. However, there is no spin polarized state in the Sc and Co doped systems. TM atoms doped phosphorene system becomes a magnetic half-metal or a magnetic semiconductor, which depends on the species of impurity atoms. The strain is a promising way to tune the magnetic moment of TM atoms doped phosphorene systems. A small biaxial strain could induce a magnetic transition from a state with magnetic moment to another state in phosphorene doped by Fe or Mn atom. For Mn doped system, the magnetic moment changes from 2 μB to 4 μB. For Fe doped system, the magnetic moment changes from 1 μB to 3 μB. The results establish the potential for black phosphorus utilization in innovative spintronic devices.

Heusler alloys containing Co and Mn are amongst the most heavily studied half metallic ferromagnets for future applications in spintronics. Using state-of-the-art electronic structure calculations, we investigate the effect of doping and disorder on their electronic and magnetic properties. Small degrees of doping by substituting Fe or Cr for Mn scarcely affect the half metallicity. A similar effect is also achieved by mixing the sublattices occupied by the Mn and sp atoms. Thus the half metallicity is a robust property of these alloys.

Results are presented from a theoretical study of the possibility of hole carrier localization and metal-insulator transitions which show up in the temperature dependences of the magnetic susceptibility χ(T) of doped copper-oxide (cuprate) compounds. The criteria for metal-insulator transitions owing to strong hole-lattice interactions and the formation of very narrow polaron bands in these materials with reduced doping level x are analyzed. It is shown that these kinds of metal-insulator transitions occur in underdoped La2-xSrxCuO4 and YBa2Cu3O6+x cuprates (i.e., for x ranging from 0.04 to 0.12). The characteristic temperature dependences χ(T) of the HTSC cuprates are found for different doping levels. These results are in good agreement with experimental data on metal-insulator transitions and the magnetic susceptibility of the HTSC cuprates.

The mechanical and tribological properties of pure MoS2, pure Au, Au-MoS2 and Ti-MoS2 coatings were evaluated and examined at a microscopic scale. The metaldoped MoS2 coatings had varying metal content, 5-10at% for Ti and 10-90% for Au. Reciprocating sliding wear tests were performed with a range of initial Hertzian contact pressures from 0.41 to 3.5 GPa and in air at two humidity levels (i.e. "low" being 3-5%RH and "high" being 30-40%RH). Titanium and gold were chosen for this study as metal additives due to their positive influence on the mechanical properties of the coating. The friction and wear behavior at the micro-scale were directly compared to tribological properties at the macro-scale, which were performed using an in situ tribometer. Reciprocating micro- and macro- wear tests were performed with spherical diamond tip (with 10 and 50 mum radii) and a sapphire tip (with a radius of 3.175 mm), respectively. The range of initial Hertzian contact pressures for macro-scale (i.e. between 0.41GPa and 1.2GPa) overlapped with that for micro-scale. However, the initial Hertzian contact diameters (2*a) were very different (i.e. 0.8-2.3 mum for micro-scale and 60-180 mum for macro-scale). It was observed that the small addition of Ti or Au to MoS2 improved the microtribological properties (i.e. lower friction and less wear) compared to pure MoS2 coatings. The improved microtribological properties with metal additions were attributed to an increase in the mechanical properties, decrease in adhesion, and a decrease in the interfacial shear strength. In terms of the different length scales, lower steady state friction was observed for macrotribology compared to microtribology. The higher friction at the micro- scale was explained by the greater adhesion effects and additional velocity accommodation modes (e.g. microplowing or plowing). The microplowing or plowing at the microscopic scale was attributed to the tip roughness and the inability to sustain a stable

The superior photoconductive behavior of a simple, cost-effective n-GaN nanorod (NR)-graphene hybrid device structure is demonstrated for the first time. The proposed hybrid structure was synthesized on a Si (111) substrate using the high-quality graphene transfer method and the relatively low-temperature metal-organic chemical vapor deposition (MOCVD) process with a high V/III ratio to protect the graphene layer from thermal damage during the growth of n-GaN nanorods. Defect-free n-GaN NRs were grown on a highly ordered graphene monolayer on Si without forming any metal-catalyst or droplet seeds. The prominent existence of the undamaged monolayer graphene even after the growth of highly dense n-GaN NRs, as determined using Raman spectroscopy and high-resolution transmission electron microscopy (HR-TEM), facilitated the excellent transport of the generated charge carriers through the photoconductive channel. The highly matched n-GaN NR-graphene hybrid structure exhibited enhancement in the photocurrent along with increased sensitivity and photoresponsivity, which were attributed to the extremely low carrier trap density in the photoconductive channel. PMID:26028318

Organic foams having a low density and very small cell size and method for producing same in either a metal-loaded or unloaded (nonmetal loaded) form are described. Metal-doped foams are produced by soaking a polymer gel in an aqueous solution of desired metal salt, soaking the gel successively in a solvent series of decreasing polarity to remove water from the gel and replace it with a solvent of lower polarity with each successive solvent in the series being miscible with the solvents on each side and being saturated with the desired metal salt, and removing the last of the solvents from the gel to produce the desired metal-doped foam having desired density cell size, and metal loading. The unloaded or metal-doped foams can be utilized in a variety of applications requiring low density, small cell size foam. For example, rubidium-doped foam made in accordance with the invention has utility in special applications, such as in x-ray lasers.

Graphene nanomeshes (GNMs), formed by creating a superlattice of pores in graphene, possess rich physical and chemical properties. Many of these properties are determined by the pore geometry. In this work, we use first principles calculations to study the magnetic and electronic properties of metal-doped nitrogen-passivated GNMs. We find that the magnetic behaviour is dependent on the pore shape (trigonal versus hexagonal) as dictated by the number of covalent bonds formed between the 3d metal and the passivating N atoms. We also find that Cr and V doped trigonal-pore GNMs, and Ti doped GNMs are the most favourable for spintronic applications. The calculated magnetic properties of Fe-doped GNMs compare well with recent experimental observations. The studied systems are useful as spin filters and chemical sensors.

The spin-polarized full potential linearized augmented plane wave method in the generalized gradient approximation is carried out for investigation on the magnetism and electronic structures of Cu-doped ZnS. We find that the Cu-doped ZnS supercell shows half-metallic ferromagnetic character with a total magnetic moment of 1.0μB per Cu. The long-range ferromagnetism in Cu-doped ZnS can be explained in terms of p-d like hybridization chain, and the Curie temperature higher than around 350 K is predicted. These results suggest that Cu-doped ZnS may be a promising half-metallic ferromagnetic material for applications in spintronics.

In this paper, we synthesized the transition metal ions (Mn, Cu, Fe) doped and co-doped ZnS nanowires (NWs) by a one-step hydrothermal method. The results showed that the solid solubility of the Fe2+ ions in the ZnS NWs was about two times larger than that of the Mn2+ or Cu2+ ions in the ZnS NWs. There was no phase transformation from hexagonal to cubic even in a large quantity transition metal ions introduced for all the samples. The Mn2+/Cu2+/Fe2+ related emission peaks can be observed in the Mn2+,Cu2+ and Fe2+ doped ZnS NWs. The ferromagnetic properties of the co-doped samples were investigated at room temperature.

Zinc oxide (ZnO), with its excellent luminescent properties and the ease of growth of its nanostructures, holds promise for the development of photonic devices. The recent advances in growth of ZnO nanorods are discussed. Results from both low temperature and high temperature growth approaches are presented. The techniques which are presented include metal-organic chemical vapour deposition (MOCVD), vapour phase epitaxy (VPE), pulse laser deposition (PLD), vapour-liquid-solid (VLS), aqueous chemical growth (ACG) and finally the electrodeposition technique as an example of a selective growth approach. Results from structural as well as optical properties of a variety of ZnO nanorods are shown and analysed using different techniques, including high resolution transmission electron microscopy (HR-TEM), scanning electron microscopy (SEM), photoluminescence (PL) and cathodoluminescence (CL), for both room temperature and for low temperature performance. These results indicate that the grown ZnO nanorods possess reproducible and interesting optical properties. Results on obtaining p-type doping in ZnO micro- and nanorods are also demonstrated using PLD. Three independent indications were found for p-type conducting, phosphorus-doped ZnO nanorods: first, acceptor-related CL peaks, second, opposite transfer characteristics of back-gate field effect transistors using undoped and phosphorus doped wire channels, and finally, rectifying I-V characteristics of ZnO:P nanowire/ZnO:Ga p-n junctions. Then light emitting diodes (LEDs) based on n-ZnO nanorods combined with different technologies (hybrid technologies) are suggested and the recent electrical, as well as electro-optical, characteristics of these LEDs are shown and discussed. The hybrid LEDs reviewed and discussed here are mainly presented for two groups: those based on n-ZnO nanorods and p-type crystalline substrates, and those based on n-ZnO nanorods and p-type amorphous substrates. Promising electroluminescence

ZnO nanoparticles doped with transition metals (Mn and Co) were prepared by a co-precipitation method. The synthesized nanoparticles were characterized using X-ray diffraction, scanning electron microscopy, energy dispersive X-rays, Fourier transform infrared spectroscopy, electron spin resonance spectroscopy and diffuse reflectance spectroscopy. The photocatalytic activities of the transition-metal-doped ZnO nanoparticles were evaluated in the degradation of methyl orange under UV irradiation. ZnO nanoparticles doped with 12 at.% of Mn and Co ions exhibited the maximum photodegradation efficiency. The experiment also demonstrated that the photodegradation efficiency of Mn-doped ZnO nanoparticles was higher than that of Co-doped ZnO nanoparticles. These results indicate that charge trapping states due to the doping were the decisive factor rather than the average particle size and energy gap. Moreover the effect of pH values on the degradation efficiency was discussed in the photocatalytic experiments using 12 at.% Mn- and Co-doped ZnO nanoparticles.

Hydrogen cyanide (HCN) adsorption on graphene doped with 5d transition metal (TM) is investigated by the first principles based on density functional theory. It is observed that Hg atom cannot be doped into graphene due to saturated valence electron configurations of 5d106s2. Three kinds of HCN adsorption configurations are investigated, in which H, C and N in HCN are close to the adsorption site, respectively. The most stable adsorption configuration is obtained by total energy optimization. HCN adsorption can be studied by adsorption energy and electron density difference. HCN can only be physisorbed on Ir, Pt and Au-doped graphenes, while chemisorption is observed for Lu, Hf, Ta, W, Re and Os-doped graphenes. The band structure is calculated by B3LYP and Generalized gradient approximation (GGA) functionals. It is observed from B3LYP method that the conductivity of Lu, Hf, Re and Os-doped graphenes does not obviously change before and after HCN adsorption. Ta and W-doped graphenes change from semiconductor to metal after adsorption of HCN molecule. The results indicate that Ta and W-doped graphenes may be a promising sensor for detecting HCN. This study provides a useful basis for understanding of a wide variety of physical properties on graphene.

ZnO nanoparticles doped with transition metals (Mn and Co) were prepared by a co-precipitation method. The synthesized nanoparticles were characterized using X-ray diffraction, scanning electron microscopy, energy dispersive X-rays, Fourier transform infrared spectroscopy, electron spin resonance spectroscopy and diffuse reflectance spectroscopy. The photocatalytic activities of the transition-metal-doped ZnO nanoparticles were evaluated in the degradation of methyl orange under UV irradiation. ZnO nanoparticles doped with 12 at.% of Mn and Co ions exhibited the maximum photodegradation efficiency. The experiment also demonstrated that the photodegradation efficiency of Mn-doped ZnO nanoparticles was higher than that of Co-doped ZnO nanoparticles. These results indicate that charge trapping states due to the doping were the decisive factor rather than the average particle size and energy gap. Moreover the effect of pH values on the degradation efficiency was discussed in the photocatalytic experiments using 12 at.% Mn- and Co-doped ZnO nanoparticles.

Titania, a wide band gap semiconductor, can generate powerful oxidants and reductants by absorbing photon energies. Titania has been extensively used in photoelectrochemical systems, such as dye-sensitized titania, a wide band gap semiconductor, can generate powerful oxidants and reductants by absorbing photon energies. To improve the photoreactivity of titania, several approaches, including doping and metal loading have been proposed. Nanocavities are isolated entities inside a solid and hence are very different from nanoporous, whose pores (often amorphous and irregular) connect together and open to the surface. Dense polyhedral nanocavities inside single-crystalline anatase titania nanorods were successfully synthesized by simply heating titanate nanorods. The size of the nanocavities is typically about 10 nm. The surfaces of the nanocavity polyhedron are determined to be the crystallographic low-index planes of the titania crystal. We found that these dense nanocavities significantly enhance the optical absorption coefficient of titania in the near-ultraviolet region, thereby providing a new approach to increasing the photoreactivity of the titania nanorods in the applications related to absorbing photons.

A Schottky barrier amorphous silicon solar cell incorporating a thin highly doped p-type region of hydrogenated amorphous silicon disposed between a Schottky barrier high work function metal and the intrinsic region of hydrogenated amorphous silicon wherein said high work function metal and said thin highly doped p-type region forms a surface barrier junction with the intrinsic amorphous silicon layer. The thickness and concentration of p-type dopants in said p-type region are selected so that said p-type region is fully ionized by the Schottky barrier high work function metal. The thin highly doped p-type region has been found to increase the open circuit voltage and current of the photovoltaic device.

Effects of doping on single-walled carbon nanotubes (SWNT) networks with different metallicity are reported through the study of sheet resistance changes upon annealing and acid treatment. SWNT film with high metallic tube content is found to have relatively good chemical stability against post treatments, as demonstrated from its stable film performance in ambient after annealing, and merely 15% reduction in sheet resistance upon sulfuric acid treatment. Conversely, film stability of SWNT film with low metallic content which comprises largely of semiconducting SWNT varies with days in ambient, and its sheet resistance changes drastically after treated with acid, indicating the extreme sensitivity of semiconducting SWNT to surrounding environment. The results suggest that annealing removes unintentional oxygen doping from the ambient and shifts the Fermi level towards the intrinsic Fermi level. Acid treatment, on the other hand, introduces physisorbed and chemisorbed oxygen and shifts the Fermi level away from the intrinsic level and increases the hole doping.

Recently, insulator-metal transition was found experimentally in Gd-doped SrTiO3 films. Here, we present first-principle investigation on the structural, electronic and magnetic properties of Sr1-xGdxTiO3 within density-function theory. The spin-polarized calculations give a diamagnetic insulator at x=0, a ferrimagnetic metal 0.125≤ x≤0.5 and a ferrimagnetic insulator x=1 and all Ti ions moments are antiparallel to Gd ions moments. Magnetic Gd-doping distorts the structures of Sr1-xGdxTiO3 films and results in ferrimagnetism. Doped electrons occupy the bottom of conduction bands so that insulator-metal transition occurs. These calculated results are in agreement with available experiments.

We report on the growth and transport properties of single crystalline Sb doped SnO2 wires grown from chemical vapour deposition. While undoped samples presented semiconducting behaviour, doped ones clearly undergo a transition from an insulating state ( d R /d T <0 ) to a metallic one ( d R /d T >0 ) around 130 -150 K depending on the doping level. Data analysis in the framework of the metal-to-insulator transition theories allowed us to investigate the underlying physics: electron-electron and electron-phonon interactions were identified as the scattering mechanisms present in the metallic phase, while the conduction mechanism of the semiconducting phase (undoped sample) was characterized by thermal activation and variable range hopping mechanisms.

The notion of metal-free catalysts is used to refer to carbon materials modified with nonmetallic elements. However, some claimed metal-free catalysts are prepared using metal-containing precursors. It is highly contested that metal residues in nitrogen-doped carbon (NC) catalysts play a crucial role in the oxygen reduction reaction (ORR). In an attempt to reconcile divergent views, a definition for truly metal-free catalysts is proposed and the differences between NC and M-Nx /C catalysts are discussed. Metal impurities at levels usually undetectable by techniques such as XPS, XRD, and EDX significantly promote the ORR. Poisoning tests to mask the metal ions reveal the involvement of metal residues as active sites or as modifiers of the electronic structure of the active sites in NC. The unique merits of both M-Nx /C and NC catalysts are discussed to inspire the development of more advanced nonprecious-metal catalysts for the ORR.

The electronic structures, formation energies, and band edge positions of anatase TiO2 doped with transition metals have been analyzed by ab initio band calculations based on the density functional theory with the planewave ultrasoft pseudopotential method. The model structures of transition metal-doped TiO2 were constructed by using the 24-atom 2 × 1 × 1 supercell of anatase TiO2 with one Ti atom replaced by a transition metal atom. The results indicate that most transition metaldoping can narrow the band gap of TiO2, lead to the improvement in the photoreactivity of TiO2, and simultaneously maintain strong redox potential. Under O-rich growth condition, the preparation of Co-, Cr-, and Ni-doped TiO2 becomes relatively easy in the experiment due to their negative impurity formation energies, which suggests that these doping systems are easy to obtain and with good stability. The theoretical calculations could provide meaningful guides to develop more active photocatalysts with visible light response. PMID:24472374

We theoretically and numerically investigate metal enhanced fluorescence of plasmonic core-shell nanoparticles doped with rare earth (RE) ions. Particle shape and size are engineered to maximize the average enhancement factor (AEF) of the overall doped shell. We show that the highest enhancement (11 in the visible and 7 in the near-infrared) is achieved by tuning either the dipolar or the quadrupolar particle resonance to the rare earth ion's excitation wavelength. Additionally, the calculated AEFs are compared to experimental data reported in the literature, obtained in similar conditions (plasmon mediated enhancement) or when a metal-RE energy transfer mechanism is involved.

Fullerene (C60) has been used extensively as an acceptor material in organic photovoltaic (OPV) cells. Other applications including n-channel organic thin film transistors (OTFT) and C60 based organic superconductors have been reported more than a decade ago. We have investigated p-doping of C60 with molybdenum oxide (MoOx) with ultra-violet photoemission spectroscopy (UPS), inverse photoemission spectroscopy (IPES) and atomic force microscopy (AFM). Both surface doping and bulk doping by MoOx are studied. It was found that the thermally evaporated MoOx inter-layer substantially increased the surface workfunction. This increased surface workfunction strongly attract electrons towards the MoOx layer at the C60/MoOx interface, resulting in strong inversion of C60. Energy levels of C60 relax gradually as the thickness of C60 increases. An exceptionally long (greater than 400 Angstrom) band bending is observed during this relaxation in C60. Such a long band bending has not been observed for other organic/MoOx interface. For the bulk doping, MoOx doping ratios from 1% to over 100% were investigated. The saturation occurs at approximately 20 %, when the highest occupied molecular level (HOMO) of C60 starts to be pinned at the Fermi level. These studies demonstrate effective ways to manipulate the electronic structures of the fullerene. This work is supported by the National Science Foundation Grant No. DMR-1303742.

The photochemical tunability of the charge-transport mechanism in metal-oxide semiconductors is of great interest since it may offer a facile but effective semiconductor-to-metal transition, which results from photochemically modified electronic structures for various oxide-based device applications. This might provide a feasible hydrogen (H)-radical doping to realize the effectively H-dopedmetal oxides, which has not been achieved by thermal and ion-implantation technique in a reliable and controllable way. In this study, we report a photochemical conversion of InGaZnO (IGZO) semiconductor to a transparent conductor via hydrogen doping to the local nanocrystallites formed at the IGZO/glass interface at room temperature. In contrast to thermal or ionic hydrogen doping, ultraviolet exposure of the IGZO surface promotes a photochemical reaction with H radical incorporation to surface metal-OH layer formation and bulk H-doping which acts as a tunable and stable highly doped n-type doping channel and turns IGZO to a transparent conductor. This results in the total conversion of carrier conduction property to the level of metallic conduction with sheet resistance of ∼16 Ω/□, room temperature Hall mobility of 11.8 cm(2) V(-1) sec(-1), the carrier concentration at ∼10(20) cm(-3) without any loss of optical transparency. We demonstrated successful applications of photochemically highly n-dopedmetal oxide via optical dose control to transparent conductor with excellent chemical and optical doping stability.

TiO2 nanorods can be used as dye-sensitized solar cells and as various sensors and photocatalysts. These nanorods are synthesized by using a thermal corrosion process in a NaOH solution at 200 °C with TiO2 powder as a source material. In the present work, the synthesis of TiO2 nanorods in anatase, rutile and Ti8O15 phases and the synthesis of TiO2 nanorods by using the sol-gel method and alkaline corrosion to incorporate silver and silver-oxide dopants are reported. The morphologies and the crystalline structures of the TiO2 nanorods are characterized using field emission scanning electron microscopy (FE-SEM), atomic force microscopy (AFM), tunneling electron microscopy (TEM) and X-ray diffraction (XRD) techniques. The obtained results show an aggregation structure at high calcining temperatures with spherical particles and with Ti-O-Ti, Ti-O and Ag-O bonds. The effects of the chemical composition and the calcining temperature on the surface topography, lattice strain and phase crystallization are studied. The activation energy (E) of nanoparticle formation in a pure state during thermal treatment is calculated.

Metal hydrides could be considered ideal solid-state hydrogen storage systems, they have light weight and high hydrogen volumetric densities, but the hydrogen desorption process requires excessively high temperatures due to their high stability. Efforts have been performed to improve their dehydrogenation properties, based on the introduction of defects, impurities and doping. We present a systematic study of the n-type (electronic) doping effects on the stability of two alkali-metal hydrides: Na1-xMgxH and Li1-xBexH. These systems have been studied within the framework of density functional perturbation theory, using a mixed-basis pseudopotential method and the self-consistent version of the virtual crystal approximation to model the doping. The full-phonon dispersions are analyzed for several doping content, paying special attention to the crystal stability. It is found a doping content threshold for each system, where they are close to dynamical instabilities, which are related to charge redistribution in interstitial zones. Applying the quasiharmonic approximation, the vibrational free energy, the linear thermal expansion and heat capacities are obtained for both hydrides systems and are analyzed as a function of the doping content. This work is partially supported by the VIEP-BUAP 2016 and CONACYT-México (No.221807) projects.

The adsorption of H2CO molecule on pristine and transition metal (Ti and V) doped graphene samples were investigated via a first-principles approach based on density functional theory. The most stable adsorption geometry, energy and charge transfer of H2CO molecule on pristine and doped graphene are discussed respectively. We have found that Ti and V dopant atoms can significantly enhance the interaction between H2CO molecule and graphene. The calculated net electron transfers, electronic density difference images and densities of states give the evidence that the H2CO molecules stay on Ti (or V) - doped graphene by chemisorption. After H2CO adsorption, there are significant changes in electronic structure near the Fermi level, for both two systems of Ti and V doped graphene. This indicates distinct changes of electron transport properties. We have also found that H2CO molecule has a larger absorption energy on V-doped graphene (1.939 eV) compared with Ti-doped graphene (1.120 eV). It is shown that the Ti-doped graphene has enough binding energy, adequate changes in electronic structure and reasonable short recovery time 10-3 s, making it a promising candidate for detecting formaldehyde gas.

Metal oxide (TiO2 or Co3O4) doped activated carbon nanofibers (ACNFs) were prepared by electrospinning. These nanofibers were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and Brunner-Emmett-Teller method (BET). The results show that the average diameters of ACNFs were within the range of 200-500 nm, and the lengths were several tens of micrometers. The specific surface areas were 1146.7 m2/g for TiO2-doped ACNFs and 1238.5 m2/g for Co3O4-doped ACNFs, respectively. The electrospun nanofibers were used for adsorption of low concentration sulfur dioxide (SO2). The results showed that the adsorption rates of these ACNFs increased with an increase in SO2 concentration. When the SO2 concentration was 1.0 μg/mL, the adsorption rates of TiO2-doped ACNFs and Co3O4-doped ACNFs were 66.2% and 67.1%, respectively. The adsorption rate also increased as the adsorption time increased. When the adsorption time was 40 min, the adsorption rates were 67.6% and 69.0% for TiO2-doped ACNFs and Co3O4-doped ACNFs, respectively. The adsorption rate decreased as the adsorption temperature increased below 60°C, while it increased as the adsorption temperature increased to more than 60°C.

Electron transport parameters such as electron effective mass, Fermi velocity of an electron and electron mobility are calculated for transition metal [manganese (Mn), cobalt (Co)]-doped armchair graphene nanoribbon (aGNR) via polar acoustical phonon [piezoelectric (PZ)] scattering and acoustical deformation potential (ADP) scattering under a high electric field and different doping concentrations. Moreover, the effect of dopant site on these electron transport parameters is also investigated. It is observed that the electron effective mass is reduced significantly in doped aGNR in comparison to pure GNR. It is observed that the net electron mobility contributed by both ADP and PZ mechanisms for Mn-doped aGNR as well as Co-doped aGNR varies in similar fashion as semiconductors wherein the net electron mobility (ADP + PZ) for Mn-doped aGNR is greater than that for the Co-doped graphene nanoribbon. Moreover, it is found that there is no impact of variation in dopant site on the electron transport parameters considered in this study.

In this work we performed the filling of single-walled carbon nanotube channels with metallic silver and copper by means of two-step synthesis including imbuing with metal nitrate aqueous solution and further annealing. It has been shown that metal insertion into the nanotube cavities results in the Fermi level upshift and the charge transfer from metal to carbon atoms, thus donor doping of single-walled carbon nanotubes takes place. At the same time, encapsulated silver has a larger donor effect on the carbon nanotubes that has been proved by Raman spectroscopy and X-ray photoelectron spectroscopy.

Adsorption of molecular oxygen with a triplet ground state on Fe-, Co-, Ni-, Ru-, Rh-, Pd-, OS-, Ir- and Pt-doped graphene is studied using density functional theory (DFT) calculations. The calculations show that O2 molecule is chemisorbed on the doped graphene sheets with large adsorption energies ranging from -0.653 eV to -1.851 eV and the adsorption process is irreversible. Mulliken atomic charge analysis of the structure shows that charge transfer from doped graphene sheets to O2 molecule. The amounts of transferred charge are between 0.375e- to 0.650e-, indicating a considerable change in the structures conductance. These results imply that the effect of O2 adsorption on transition metal-doped graphene structures can alter the possibility of using these materials as a toxic-gas (carbon monoxide, hydrogen fluoride, etc.) sensor.

The structural, electronic and magnetic properties of arsenene doped with five different transition-metal (TM) atoms (TM = Co, Cu, Mn, Fe, and Ni) are investigated using the density functional theory. Magnetism is observed in the cases of Cu, Mn, Fe, and Ni. Among these four magnetic systems, the Ni-doped system is the most easily formed. Hence, we study the ferromagnetic (FM) interaction in two-Ni-doped arsenene. It is found that the p-d hybridization mechanism results in the ferromagnetic state. However, the FM interaction is obviously depressed by the increasing Ni-Ni distance, which could be well explained by the Zener-Ruderman-Kittel-Kasuya-Yosida (RKKY) theory. Moreover, exotic phenomena appear in the two-Mn-doped system. Both nonmagnetic and ferromagnetic states are observed.

Magnetic properties of transition-metal (TM) atoms (TM=Co, Cu, Mn, Fe, and Ni) doped ReS2 monolayer are investigated by first-principles calculations. It is found that magnetism appears in the cases of Co, Fe, and Ni. Among all the samples, the Co-doped system has the largest magnetic moment. Therefore, we further study the interaction in the two-Co-doped system. Our results show that the interaction between two Co atoms is always ferromagnetic (FM), but such FM interaction is obviously depressed by the increasing Co-Co distance, which is well described by a simple Heisenberg model based on the Zener theory. Our results provide useful insight for promising applications of TM-doped ReS2 monolayer in the future.

Wide band gap II-VI nanostructures are important building blocks for new-generation electronic and optoelectronic devices. However, the difficulty of realizing p-type conductivity in these materials via conventional doping methods has severely handicapped the fabrication of p-n homojunctions and complementary circuits, which are the fundamental components for high-performance devices. Herein, by using first-principles density functional theory calculations, we demonstrated a simple yet efficient way to achieve controlled p-type doping on II-VI nanostructures via surface charge transfer doping (SCTD) using high work function transition metal oxides such as MoO3, WO3, CrO3, and V2O5 as dopants. Our calculations revealed that these oxides were capable of drawing electrons from II-VI nanostructures, leading to accumulation of positive charges (holes injection) in the II-VI nanostructures. As a result, Fermi levels of the II-VI nanostructures were shifted toward the valence band regions after surface modifications, along with the large enhancement of work functions. In situ ultraviolet photoelectron spectroscopy and X-ray photoelectron spectroscopy characterizations verified the significant interfacial charge transfer between II-VI nanostructures and surface dopants. Both theoretical calculations and electrical transfer measurements on the II-VI nanostructure-based field-effect transistors clearly showed the p-type conductivity of the nanostructures after surface modifications. Strikingly, II-VI nanowires could undergo semiconductor-to-metal transition by further increasing the SCTD level. SCTD offers the possibility to create a variety of electronic and optoelectronic devices from the II-VI nanostructures via realization of complementary doping.

direction has been achieved and was published recently in Nature-Chemistry [11a]. Specifically, a Pd coin doped with 1% cinchonidine alkaloid was shown...removed; the alkaloid modifier is necessary, in this case, for obtaining enantioselective catalysis. References [1] H. Behar-Levy and D. Avnir

Well-crystallizedβ-SiC nanorods grown on electrospun nanofibers were synthesized by carbothermal reduction of Tb doped SiO2(SiO2:Tb) nanofibers at 1,250 °C. The as-synthesized SiC nanorods were 100–300 nm in diameter and 2–3 μm in length. Scanning electron microscopy (SEM) results suggested that the growth of the SiC nanorods should be governed by vapor-liquid-solid (VLS) mechanism with Tb metal as catalyst. Tb(NO3)3particles on the surface of the electrospun nanofibers were decomposed at 500 °C and later reduced to the formation of Tb nanoclusters at 1,200 °C, and finally the formation of a Si–C–Tb ally droplet will stimulate the VLS growth at 1,250 °C. Microstructure of the nanorod was further investigated by transmission electron microscopy (TEM). It was found that SiC <111> is the preferred initial growth direction. The liquid droplet was identified to be Si86Tb14, which acted as effective catalyst. Strong green emissions were observed from the SiC nanorod samples. Four characteristic photoluminescence (PL) peaks of Tb ions were also identified. PMID:20596383

How Mott insulators acquire metallicity upon the introduction of extra carriers lies at the heart of correlated electron physics. The evolution of the electronic structure and low energy dynamics in the ultra-low doped region where the Mottness begins to break down is a critical place to study this physics. We report ARPES studies of the Rh and La doped Sr2IrO4 and show the appearance and evolution of a pseudogap and Fermi arcs. Further more we present evidence how the Mott gap breaks down with a profound change in the band structure. The experimental results in the doped iridates resemble those observed in the cuprate systems, which are prototype Mott insulators, and suggest we could establish a series of signatures that occur in the metal insulator transition. Now at Los Alamos National Lab.

Structural and optical properties of bare ZnO nanorods, ZnO-encapsulated ZnO nanorods, and Cr-doped ZnO-encapsulated ZnO nanorods have been investigated. Encapsulated ZnO nanorods were grown using a simple two-stage method in which ZnO nanorods were first grown on a glass substrate directly from a hydrothermal bath, then encapsulated with a thin layer of Cr-doped ZnO by dip coating. Comparative study of x-ray diffraction patterns showed that Cr was successfully incorporated into the shell layer of ZnO nanorods. Moreover, energy-dispersive x-ray spectroscopy confirmed presence of Cr in this sample. It was observed that the thickness of the shell layer around the core of the ZnO nanorods was at least about 20 nm. Transmission electron microscopy of bare ZnO nanorods revealed single-crystalline structure. Based on optical results, both the encapsulation process and addition of Cr dopant decreased the optical bandgap of the samples. Indeed, the optical bandgap values of Cr-doped ZnO-encapsulated ZnO nanorods, ZnO-encapsulated ZnO nanorods, and bare ZnO nanorods were 2.89 eV, 3.15 eV, and 3.34 eV, respectively. The ultraviolet (UV) parameters demonstrated that incorporation of Cr dopant into the shell layer of ZnO nanorods considerably facilitated formation and transportation of photogenerated carriers, optimizing their performance as a practical UV detector. As a result, the photocurrent of the Cr-doped ZnO-encapsulated ZnO nanorods was the highest (0.6 mA), compared with ZnO-encapsulated ZnO nanorods and bare ZnO nanorods (0.21 mA and 0.06 mA, respectively).

First-principles calculations are performed to study the geometry, electronic structure and magnetic properties of light non-metallic atom-doped graphene (B, N, O and F). The planar structure and the quasi-linear energy dispersion near the Dirac point remain through doping with B and N atoms, by which p-type doping and n-type doping graphene are respectively induced. A bandgap of about 0.5 eV is generated through O doping, and geometrically the O atom is also in the graphene plane. No magnetic moment is detected in B- , N- and O-doped graphene. For F doping, the F atom bonds with one of the carbon atoms close to the vacancy, with the other two carbon atoms undergoing a Jahn-Teller distortion. A weak polarized magnetic moment of 0.71 µ(B) is detected through F doping.

A hydrogen storage material having improved hydrogen absorbtion and desorption kinetics is provided by adding graphite to a complex hydride such as a metal-doped alanate, i.e., NaAlH.sub.4. The incorporation of graphite into the complex hydride significantly enhances the rate of hydrogen absorbtion and desorption and lowers the desorption temperature needed to release stored hydrogen.

BiVO4 has become the top-performing semiconductor among photoanodes for photoelectrochemical water oxidation. However, BiVO4 photoanodes are still limited to a fraction of the theoretically possible photocurrent at low applied voltages because of modest charge transport properties and a trade-off between light absorption and charge separation efficiencies. Here, we investigate photoanodes composed of thin layers of BiVO4 coated onto Sb-doped SnO2 (Sb:SnO2) nanorod-arrays (Sb:SnO2/BiVO4 NRAs) and demonstrate a high value for the product of light absorption and charge separation efficiencies (ηabs × ηsep) of ∼51% at an applied voltage of 0.6 V versus the reversible hydrogen electrode, as determined by integration of the quantum efficiency over the standard AM 1.5G spectrum. To the best of our knowledge, this is one of the highest ηabs × ηsep efficiencies achieved to date at this voltage for nanowire-core/BiVO4-shell photoanodes. Moreover, although WO3 has recently been extensively studied as a core nanowire material for core/shell BiVO4 photoanodes, the Sb:SnO2/BiVO4 NRAs generate larger photocurrents, especially at low applied voltages. In addition, we present control experiments on planar Sb:SnO2/BiVO4 and WO3/BiVO4 heterojunctions, which indicate that Sb:SnO2 is more favorable as a core material. These results indicate that integration of Sb:SnO2 nanorod cores with other successful strategies such as doping and coating with oxygen evolution catalysts can move the performance of BiVO4 and related semiconductors closer to their theoretical potential.

We have investigated the structural and magnetic properties of Li doped graphitic carbon nitride (g-C4N3) using the van der Waals density functional theory. A free standing g-C4N3 was known to show a half metallic state with buckling geometry, but this feature completely disappears in the presence of Li doping. Besides this structural modification, very interestingly, we have obtained that the Li doped g-C4N3 shows dramatic change in its electronic structure. Both ferromagnetic and nonmagnetic states are almost degenerated in one Li atom doped system. However, the transition from half metallic state to semiconductor is observed with further increase of Li concentration and the calculated energy gap is 1.97 eV. We found that Li impurity plays as a donor element and charge transfer from the Li atom to neighboring N atoms induces a band gap. Overall, we have observed that the electronic and magnetic properties of g-C4N3 are substantially modified by Li doping.

Nitrogen-doped graphene (N/GR) has been considered as active metal-free electrocatalysts for oxygen reduction reaction (ORR). However, the nitrogen (N) doping efficiency is very low and only few N atoms are doped into the framework of GR. To boost the N doping efficiency, in this work, a confined pyrolysis method with high N doping efficiency is used for the preparation of cobalt nanoparticles/nitrogen-doped GR (Co/N/GR). Under the protection of SiO2, the inorganic ligand NH3 in cobalt amine complex ([Co(NH3)6](3+)) is trapped in the confined space and then can be effectively doped into the framework of GR without the introduction of any carbon residues. Meanwhile, due to the redox reaction between the cobalt ions and carbon atoms of GR, Co nanoparticles are supported into the framework of N/GR. Due to prevention of GR layer aggregation with SiO2, the Co/N/GR with high dispersion provides sufficient surface area and maximum opportunity for the exposure of Co nanoparticles and active sites of N dopant. By combination of enhanced N doping efficiency, Co nanoparticles and high dispersion of GR sheets, the Co/N/GR is remarkably active, cheap and selective noble-metal free catalysts for ORR.

The lowest-energy structures of neutral and cationic GenM (n = 9, 10; M = Si, Li, Mg, Al, Fe, Mn, Pb, Au, Ag, Yb, Pm and Dy) clusters were studied by genetic algorithm (GA) and first-principles calculations. The calculation results show that doping of the metal atoms and Si into Ge9 and Ge10 clusters is energetically favorable. Most of the metal-doped Ge cluster structures can be viewed as adding or substituting metal atom on the surface of the corresponding ground-state Gen clusters. However, the neutral and cationic FeGe9,10,MnGe9,10 and Ge10Al are cage-like with the metal atom encapsulated inside. Such cage-like transition metaldoped Gen clusters are shown to have higher adsorption energy and thermal stability. Our calculation results suggest that Ge9,10Fe and Ge9Si would be used as building blocks in cluster-assembled nanomaterials because of their high stabilities.

The lowest-energy structures of neutral and cationic Ge nM (n = 9, 10; M = Si, Li, Mg, Al, Fe, Mn, Pb, Au, Ag, Yb, Pm and Dy) clusters were studied by genetic algorithm (GA) and first-principles calculations. The calculation results show that doping of the metal atoms and Si into Ge9 and Ge10 clusters is energetically favorable. Most of the metal-doped Ge cluster structures can be viewed as adding or substituting metal atom on the surface of the corresponding ground-state Gen clusters. However, the neutral and cationic FeGe9,10,MnGe9,10 and Ge10Al are cage-like with the metal atom encapsulated inside. Suchmore » cage-like transition metaldoped Gen clusters are shown to have higher adsorption energy and thermal stability. Our calculation results suggest that Ge9,10Fe and Ge9Si would be used as building blocks in cluster-assembled nanomaterials because of their high stabilities.« less

In the past decade, room temperature ferromagnetism was often observed in transition metaldoped semiconductors, which were claimed as diluted magnetic semiconductors (DMS). Nowadays intensive activities are devoted to clarify wether the observed ferromagnetism stems from carrier mediated magnetic impurities, ferromagnetic precipitates, or spinodal decomposition. In this paper, we have correlated the structural and magnetic properties of transition metaldoped ZnO, TiO2, and Si, prepared by ion implantation. Crystalline precipitates, i.e., transition metal (Co, Ni) and Mn-silicide nanocrystals, are responsible for the magnetism. Additionally due to their orientation nature with respect to the host, these nanocrystals in some cases are not detectable by conventional x-ray diffraction (XRD). This nature results in the pitfall of using XRD to exclude magnetic precipitates in DMS materials.

Nitrogen-doped graphene (N-graphene) was synthesized by chemical vapor deposition of methane in the presence of ammonia. The resultant N-graphene was demonstrated to act as a metal-free electrode with a much better electrocatalytic activity, long-term operation stability, and tolerance to crossover effect than platinum for oxygen reduction via a four-electron pathway in alkaline fuel cells. To the best of our knowledge, this is the first report on the use of graphene and its derivatives as metal-free catalysts for oxygen reduction. The important role of N-doping to oxygen reduction reaction (ORR) can be applied to various carbon materials for the development of other metal-free efficient ORR catalysts for fuel cell applications, even new catalytic materials for applications beyond fuel cells.

Chemical synthesis of graphene relies on the usage of various chemical reagents. The initial synthesis step, in which graphite is oxidized to graphite oxide, is achieved by a combination of chemical oxidants and acids. A subsequent chemical reduction step eliminates/reduces most oxygen functionalities to yield graphene. We demonstrate here that these chemical treatments significantly contaminate graphene with heteroatoms/metals, depending on the procedures followed. Contaminations with heteroatoms (N, B, Cl, S) or metals (Mn, Al) were present at relatively high concentrations (up to 3 at%), with their chemical states dependent on the procedures. Such unintentional contaminations (unwanted doping) during chemical synthesis are rarely anticipated and reported, although the heteroatoms/metals may alter the electronic and catalytic properties of graphene. In fact, the levels of unintentionally introduced contaminants on graphene are often higher than typical levels found on intentionally doped graphene. Our findings are important for scientists applying chemical methods to prepare graphene.

Structural and electronic properties of 3d transition metal Sc, Ti, Cr and Mn incorporated 2H-WSe2 have been systematically investigated by first-principles calculations based on density functional theory. The calculated formation energies reveal that all the doped systems are thermodynamically more favorable under Se-rich condition than W-rich condition. The geometry structures almost hold that of the pristine 2H-WSe2 albeit with slight lattice distortion. More importantly, the electronic properties have been significantly tuned by the dopants, i.e., metal and semimetal behavior has been found in Sc, Ti and Mn-doped 2H-WSe2, respectively, semiconducting nature with narrowed band gap is expected in Cr-doped case, just as that of the pristine 2H-WSe2. In particular, magnetic character is realized by incorporation of Mn impurity with a total magnetic moment of 0.96 μB. Our results suggest chemical doping is an effective way to precisely tailor the electronic structure of layered transition metal dichalcogenide 2H-WSe2 for target technological applications.

Coupled cluster and density functional theory calculations have been used to assess the role of the transition metal spin state upon the energetic favorability of hydride formation within small, transition metaldoped, magnesium clusters. The spin state is found to modulate the occupation of bonding and anti-bonding orbitals, thus having a large effect upon both geometric and energetic parameters. This chemical description provides a potential theoretical basis for unexplained experimental observations, and indicates a mechanism for using an external magnetic field to control the thermodynamics of H2 sorption and desorption in metal hydrides.

A simple and versatile approach has been developed to synthesize multi-walled carbon nanotubes/metal-doped ZnO nanohybrid materials (MWNT/M-doped ZnO) by means of the co-deposition method. The experimental results illuminate that MWNTs can be modified by metal-doped ZnO nanoparticles at 450 °C, such as Mn, Mg, and Co elements. Furthermore, the MWNT/Mg-doped ZnO hybrids have been proven to have a high photocatalytic ability for methyl orange (MO), in which the degraded rate for MO reaches 100 % in 60 min. The enhancement in photocatalytic activity is attributed to the excellent electriconal property of MWNTs and Mg-doping. The resultant MWNT/Mg-doped ZnO nanohybrids have potential applications in photocatalysis and environmental protection.

A nitrogen-doped porous carbon material (N@MOG-C) was prepared by simple pyrolysis of polypyrrole-doped Al-based metal-organic gel (PPy@MOG) at 800 °C. The N@MOG-C possessed a uniform three-dimensional (3-D) interconnected mesoporous structure with a high surface area of 1542.6 m(2) g(-1) and a large pore volume of 0.76 cm(3) g(-1). By using an ionic liquid (IL) to immobilize N@MOG-C on electrode surface, the N@MOG-C was further used for sensitive detection of heavy metal ion. The doping of nitrogen-endowed N@MOG-C with faster electron transfer kinetics than other carbon materials such as MOG-C, multiwalled carbon nanotubes, and graphene. The N@MOG-C-modified electrode showed a high effective area, because of the porous structure. Under optimized conditions, the N@MOG-C-based sensor could detect Cd ions present in concentrations of 0.025-5 μM, with a detection limit of 2.2 nM. The mesoporous structure, fast electron transfer ability, and simple and green synthesis of N@MOG-C made it a promising electrode material for practical applications in heavy-metal-ion sensing.

Plasmonic materials that strongly interact with light are ideal candidates for designing subwavelength photonic devices. We report on direct coupling of terahertz waves in metallicnanorods by observing the resonant transmission of surface plasmon polariton waves through lithographically patterned films of silver nanorod (100 nm in diameter) micro-hole arrays. The best enhancement in surface plasmon resonant transmission is obtained when the nanorods are perfectly aligned with the electric field direction of the linearly polarized terahertz wave. This unique polarization-dependent propagation of surface plasmons in structures fabricated from nanorod films offers promising device applications. We conclude that the anisotropy of nanoscale metallic rod arrays imparts a material anisotropy relevant at the microscale that may be utilized for the fabrication of plasmonic and metamaterial based devices for operation at terahertz frequencies.

The liquid-phase synthesis of metal oxide nanoparticles in organic solvents under exclusion of water is nowadays a well-established alternative to aqueous sol-gel chemistry. In this article, we highlight some of the advantages of these routes based on selected examples. The first part reviews some recent developments in the synthesis of ternary metal oxide nanoparticles by surfactant-free nonaqueous sol-gel routes, followed by the discussion of the morphology-controlled synthesis of lanthanum hydroxide nanoparticles, and the presentation of structural peculiarities of manganese oxide nanoparticles with an ordered Mn vacancy superstructure. These examples show that nonaqueous systems, on the one hand, allow the preparation of compositionally complex oxides, and, on the other hand, make use of the organic components (initially present or formed in situ) in the reaction mixture to tailor the morphology. Furthermore, obviously even the crystal structure can differ from the corresponding bulk material like in the case of MnO nanoparticles. In the second part of the paper we present original results regarding the synthesis of dilute magnetic semiconductor TiO{sub 2} nanoparticles doped with cobalt and iron. The structural characterization as well as the magnetic properties with special attention to the doping efficiency is discussed. - Graphical abstract: In the first part of this article, nonaqueous sol-gel routes to ternary metal oxide nanoparticles are briefly reviewed, followed by the discussion of the morphology-controlled synthesis of lanthanum hydroxide nanoparticles, and the appearance of an unprecedented superstructure in MnO nanoparticles. In the second part, doping experiments of TiO{sub 2} with Fe and Co are presented, along with their characterization including magnetic measurements.

The study of the magnetism and optical properties of semiconductor materials by defect engineering has attracted much attention because of their potential uses in spintronic and optoelectronic devices. In this paper, first-principle calculations discloses that cationic vacancy formation energy of the doped wurtzite materials can be sharply decreased due to alkali metal dopants and shows that their magnetic properties strongly depend on defect and doping concentration. This effect can be ascribed to the volume change induced by foreign elements doped into the host system and atomic population's difference. The symmetric deformation induced by biaxial strain can further regulate this behavior. Our results suggest that the formation of cationic vacancy can be tailored by strain engineering and dopants incorporation.

First-principles calculations were performed to investigate the phase stability and transition within four monolayer transition-metal dichalcogenide (TMD) systems, i.e., MX{sub 2} (M = Mo or W and X = S or Se) under coupled electron doping and lattice deformation. With the lattice distortion and electron doping density treated as state variables, the energy surfaces of different phases were computed, and the diagrams of energetically preferred phases were constructed. These diagrams assess the competition between different phases and predict conditions of phase transitions for the TMDs considered. The interplay between lattice deformation and electron doping was identified as originating from the deformation induced band shifting and band bending. Based on our findings, a potential design strategy combining an efficient electrolytic gating and a lattice straining to achieve controllable phase engineering in TMD monolayers was demonstrated.

Many studies have investigated techniques to improve the bending performance of ionic polymer-metal composite (IPMC) actuators, including 'doping' of metal particles in the polymer membrane usually by means of physical processes. This study is mainly focused on the characterization of the physical, electrochemical and electromechanical properties of TiO2-doped ionic polymer membranes and IPMCs prepared by the sol-gel method, which results in a uniform distribution of the particles inside the polymer membrane. X-ray and UV-visible spectra indicate the presence of anatase-TiO2 in the modified membranes. TiO2-doped membranes (0.16 wt%) exhibit the highest level of water uptake. The glass transition temperature of these membranes, measured using differential scanning calorimetry (DSC), increases with the increase of the amount of TiO2 in the membrane. Dynamic mechanical analysis (DMA) demonstrated that the storage modulus of dried TiO2-doped ionic polymer membranes increases as the amount of TiO2 in the membrane increases, whereas the storage modulus of hydrated samples is closely related to the level of water uptake. Electrochemical impedance spectroscopy (EIS) shows that the conductivity of TiO2-doped membranes decreases with increasing TiO2 content in spite of an internal resistance drop in the samples. Above all, bending deflection of TiO2-doped IPMC decreased with higher TiO2 content in the membrane while the blocking force of each sample increased with the higher TiO2 content. Additionally, it was determined that the lifetime of IPMC is strongly dependent on the level of water uptake.

Nanoparticle synthesis within metal-organic frameworks (MOFs) is performed by the adsorption of suitable precursor molecules for the metal component and subsequent decomposition to the composite materials nanoparticles@MOF. This chapter will review different approaches of loading MOFs with more complex organic molecules and metal-organic precursor molecules. The related reactions inside MOFs are discussed with a focus on stabilizing reactive intermediates in the corresponding cavities. The syntheses of metal and metal oxide nanoparticles inside MOFs are reviewed, and different synthetic routes compared. Emphasis is placed on the micro structural characterization of the materials nanoparticles@MOF with a particular focus on the location of embedded nanoparticles using TEM methods. Some first examples of applications of the doped MOFs in heterogeneous catalysis and hydrogen storage are described.

Systems and methods for use of magnesium hydroxide, either directly or through one or more precursors, doped with a divalent or trivalent metal cation, for removing arsenic from drinking water, including water distribution systems. In one embodiment, magnesium hydroxide, Mg(OH).sub.2 (a strong adsorbent for arsenic) doped with a divalent or trivalent metal cation is used to adsorb arsenic. The complex consisting of arsenic adsorbed on Mg(OH).sub.2 doped with a divalent or trivalent metal cation is subsequently removed from the water by conventional means, including filtration, settling, skimming, vortexing, centrifugation, magnetic separation, or other well-known separation systems. In another embodiment, magnesium oxide, MgO, is employed, which reacts with water to form Mg(OH).sub.2. The resulting Mg(OH).sub.2 doped with a divalent or trivalent metal cation, then adsorbs arsenic, as set forth above. The method can also be used to treat human or animal poisoning with arsenic.

We report theoretical calculations of the mode fields of high index lead silicate and silicon nano fibers, and show that their strong longitudinal component enables efficient excitation of surface plasmons within a silver nanorod placed at the fiber tip. An excitation efficiency 1600 times higher than that of the standard single mode fibers has been achieved using a 350nm diameter silicon fiber at 1.1μm wavelength, while a factor of 640 times higher efficiency is achieved for a 400nm diameter lead silicate F2 glass fiber. The strong localized field emerging from the end of the rod serves as a nano-scale source with adjustable beam width, and such sources offer a new approach to high-resolution microscopy, particle manipulation and sensing.

Density functional theory slab calculations were performed to investigate the adsorption and dissociation of CO over pure and M-doped Ni(211) (M = Fe, Co, Ru and Rh) with the aim to elucidate the effect of transition metaldoping for CO activation. Doping the step edge of Ni(211) with Fe, Co and Ru is found to enhance the binding of CO in the initial state (IS) (in the sequence by the improvement degree: Fe > Ru > Co) as well as the co-adsorption of C and O in the final state (FS) (Ru > Fe > Co). In contrast, Rh doping is unfavorable both in the IS and in the FS. Analysis of the overall potential energy surfaces (PES) suggests CO dissociation is facilitated by Fe, Ru and Co doping both kinetically and thermodynamically, wherein Fe and Ru behave extraordinary. Interestingly, Fe substitute is slightly superior to Ru in kinetics whereas the contrary is the case in thermodynamics. Rh doping elevates the energy height from 0.97 eV on Ni(211) to 1.32 eV and releases 0.39 eV less heat relative to Ni(211), again manifesting a negative effect. Besides the classical Brønsted-Evans-Polanyi relationship, we put forward another two neat linear relations, which can well describe the feature of CO dissociation. The differences of CO adsorption and activation in the IS over pure and doped Ni(211) surfaces are rationalized via electronic structure analysis. The findings presented herein are expected to provide theoretical guidance for catalyst design and optimization in relevant processes.

We have developed a generalized seeded-growth methodology for the synthesis of monodisperse metal-doped plasmonic oxide heterodimer nanocrystals (NCs) with a near-unity morphological yield. Using indium-doped cadmium oxide (ICO) as an example, we show that a wide variety of preformed metal NCs (Au, Pt, Pd, FePt, etc.) can serve as the seeds for the tailored synthesis of metal-ICO heterodimers with exquisite size, shape, and composition control, facilitated by the delayed nucleation mechanism of the CdO phase. The metal-ICO heterodimers exhibit broadly tunable near-infrared localized surface plasmon resonances, and dual plasmonic bands are observed for Au-ICO heterodimers. We further demonstrate that the oxide domain of the Au-ICO heterodimers can be selectively and controllably transformed into a series of partially and completely hollow cadmium chalcogenide nanoarchitectures with unprecedented structural complexity, leaving the metal domain intact. Our work not only represents an exciting addition to the rapidly expanding library of chemical reactions that produce colloidal hybrid NCs, but it also provides a general route for the bottom-up chemical design of multicomponent metal-oxide-semiconductor NCs in a rational and sequential manner.

Despite metal hydrides light weight and high hydrogen volumetric densities, the Hydrogen desorption process requires excessively high temperatures due to their high stability. Attempts for improvement the hydrogenation properties have been focus on the introduction of defects, impurities and doping on the metal hydride. We present a systematic study of the electronic doping effects on the stability of a model system, NaH doped with magnesium, forming the alloying system Na1-xMgxH. We use the density functional theory (DFT) and the self-consistent version of the virtual crystal approximation (VCA) to model the doping of NaH with Mg. The evolution of the ground state structural and electronic properties is analyzed as a function of Mg-content. The full-phonon dispersion, calculated by the linear response theory (LRT) and density functional perturbation theory (DFPT), is analyzed for several Mg-concentrations, paying special attention to the crystal stability and the correlations with the electronic structure. Applying the quasiharmonic approximation (QHA), the free energy from zero-point motion is obtained, and its influence on the properties under study is analyzed. This work is partially supported by the VIEP-BUAP (OMPS-EXC14-I) and CONACYT-Mexico (No. 221807) projects.

Recently, two-dimensional transition metal dichalcogenides (TMDCs) have received tremendous attention in many fields including biomedicine. Herein, we develop a general method to dope different types of metal ions into WS2 nanoflakes, a typical class of TMDCs, and choose Gd(3+)-doped WS2 (WS2:Gd(3+)) with polyethylene glycol (PEG) modification as a multifunctional agent for imaging-guided combination cancer treatment. While WS2 with strong near-infrared (NIR) absorbance and X-ray attenuation ability enables contrasts in photoacoustic (PA) imaging and computed tomography (CT), Gd(3+) doping offers the nanostructure a paramagnetic property for magnetic resonance (MR) imaging. As revealed by trimodal PA/CT/MR imaging, WS2:Gd(3+)-PEG nanoflakes showed efficient tumor homing after intravenous injection. In vivo cancer treatment study further uncovered that WS2:Gd(3+)-PEG could not only convert NIR light into heat for photothermal therapy (PTT) but also enhance the ionizing irradiation-induced tumor damage to boost radiation therapy (RT). Owing to the improved tumor oxygenation after the mild PTT, the combination of PTT and RT induced by WS2:Gd(3+)-PEG resulted in a remarkable synergistic effect to destroy cancer. Our work highlights the promise of utilizing inherent physical properties of TMDC-based nanostructures, whose functions could be further enriched by elementary doping, for applications in multimodal bioimaging and synergistic cancer therapy.

3d-metal (Me) doped LiMn{sub 2}O{sub 4} thin films were deposited by rf magnetron sputtering of Li[Mn{sub 1.9}Me{sub 0.1}]O{sub 4} targets in Ar + N{sub 2} and Ar + O{sub 2} gas mixtures and annealed at 750{degrees}C in O{sub 2} for 1 h. From XRD measurements, the structure of the Me-doped thin film was dependent upon the element and the deposition conditions. The doping level of Me/Mn of cubic phase was less than 0.1 by EDX measurements. The Ti-LiMn{sub 2}O{sub 4} films exhibited a capacity close to theoretical for stoichiometric LiMn{sub 2}O{sub 4}. This improvement at 4 V comes at the expense of the capacity at 5 V. Cells with Ti-doped films exhibited the same low capacity fade as those with undoped LiMn{sub 2}O{sub 4} cathodes. Similar electrochemical changes were observed with the Cr- and Zn-LiMn{sub 2}O{sub 4} films. The discharge capacities above 4.5 V for the Ni-doped films were about equal to those below 4.5 V, and the thin-film cells could be cycled reversibility between 3.5 and 5.3 V.

The amount of dopant concentration, alongwith the choice of dopant, is one of the most conducive factor for the favourable outcome for light driven activities of a material. The present paper reports on the synthesis of zinc oxide nanorodsdoped with different concentrations of copper (Cu-ZnO) by simple, low-cost mechanical assisted thermal decomposition process. The as synthesized samples were tested for visible light driven photo-electrochemical (PEC) and photocatalytic activities on various hazardous dyes using methylene blue (MB), methyl orange and mixed green dye (methyl thymol blue + methylene blue). The study helped us to reveal that highest degradation efficiency was achieved for Cu concentration of 5% in ZnO on MB (91.1% degradation in 40 min). Compared to pure ZnO, the photoactivity of 5% Cu-ZnO composites shows higher photodegradation of dyes. Moreover, the photocatalytic results were found consistent with PEC studies which showed maximum current generation of +9.4 mA for 5% Cu-ZnO (carried out under dark and illumination condition). The mechanism for this enhanced photoactivity has been proposed based on the relationship established between oxygen vacancies and defects generation in the material due to different doping concentrations that directly influence its photocatalytic efficiency.

We explored the electronic and magnetic properties of 1T-HfS2 doped by transition metal (TM) atom using the first-principles calculation. We doped the transition metal atoms from the IIIB to VIB groups in nonmagnetic 1T-HfS2. Numerical results show that the pristine 1T-HfS2 is a semiconductor with indirect gaps of 1.250 eV. Magnetism can be observed for V, Cr, Mn, Fe, Co, and Cu doping. The polarized charges mainly arise from the localized 3d electrons of the TM atom. The strong p-d hybridization was found between the 3d orbitals of TM and 3p orbitals of S. The substituted 1T-HfS2 can be a metal, semiconductor or half-metal. Analysis of the band structure and magnetic properties indicates that TM-doped HfS2 (TM = V, Fe, Cu) are promising systems to explore two-dimensional diluted magnetic semiconductors. The formation energy calculations also indicate that it is energetically favorable and relatively easier to incorporate transition metal atom into the HfS2 under S-rich experimental conditions. In contrast, V-doped HfS2 has relatively wide half-metallic gap and low formation energy. So V-doped 1T-HfS2 is ideal for spin injection, which is important for application in semiconductor spintronics.

Thin films of doped VO2 were deposited, analyzed, and optimized with regard to their solar energy transmittance (Tsol) and visible/luminous light transmittance (Tlum) which are important parameters in the context of smart window applications in buildings. The doping with alkaline earth metals (AEM) like Mg, Ca, Sr, or Ba increased both Tsol and Tlum due to a bandgap widening and an associated absorption edge blue-shift. Thereby, the brown-yellowish color impression of pure VO2 thin films, which is one major hindrance limiting the usage of VO2 as thermochromic window coating, was overcome. Transparent thin films with excellent switching behavior were prepared by sputtering. Highly doped V1-xMexO2 (Me = Ca, Sr, Ba) kept its excellent thermochromic switching behavior up to x(Me) = Me/(Me + V) = 10 at. % doping level, while the optical bandgap energy was increased from 1.64 eV for undoped VO2 to 2.38 eV for x(Mg) = 7.7 at. %, 1.85 eV for x(Ca) = 7.4 at. %, 1.84 eV for x(Sr) = 6.4 at. % and 1.70 eV for x(Ba) = 6.8 at. %, as well as the absorption edge is blue shifted by increasing AEM contents. Also, the critical temperature ϑc, at which the semiconductor-to-metal transition (SMT) occurs, was decreased by AEM doping, which amounted to about -0.5 K/at. % for all AEM on average. The critical temperature was determined by transmittance-temperature hysteresis measurements. Furthermore, Tsol and Tlum were calculated and were found to be significantly enhanced by AEM doping. Tlum increased from 32.0% in undoped VO2 to 43.4% in VO2 doped with 6.4 at. % Sr. Similar improvements were found for other AEM. The modulation of the solar energy transmittance ΔTsol, which is the difference of the Tsol values in the low and high temperature phase, was almost constant or even slightly increased when the doping level was increased up to about 10 at. % Ca, Sr, or Ba.

Graphene has proven to be a promising material for transparent flexible electronics. In this study, we report the development of a transfer and doping scheme of large-area chemical vapour deposited (CVD) graphene. A technique to transfer the as-grown material onto mechanically flexible and optically transparent polymeric substrates using an ultraviolet adhesive (UVA) is outlined, along with the temporal stability of the sheet resistance and optical transparency following chemical doping with various metal chlorides (Mx Cly The sheet resistance (RS ) and 550 nm optical transparency (%T550 ) of the transferred un-doped graphene was 3.5 kΩ sq(-1) (±0.2 kΩ sq(-1) ) and 84.1 % (±2.9 %), respectively. Doping with AuCl3 showed a notable reduction in RS by some 71.4 % (to 0.93 kΩ sq(-1) ) with a corresponding %T550 of 77.0 %. After 200 h exposure to air at standard temperature and pressure, the increase in RS was found to be negligible (ΔRS AuCl3 =0.06 kΩ sq(-1) ), indicating that, of the considered Mx Cly species, AuCl3 doping offered the highest degree of time stability under ambient conditions. There appears a tendency of increasing RS with time for the remaining metal chlorides studied. We attribute the observed temporal shift to desorption of molecular dopants. We find that desorption was most significant in RhCl3 -doped samples whereas, in contrast, after 200 h in ambient conditions, AuCl3 -doped graphene showed only marginal desorption. The results of this study demonstrate that chemical doping of UVA-transferred graphene is a promising means for enhancing large-area CVD graphene in order to realise a viable platform for next-generation optically transparent and mechanically flexible electronics.

A new class of solid state laser crystals and lasers are formed of transition metaldoped sulfide, selenide, and telluride host crystals which have four fold coordinated substitutional sites. The host crystals include II-VI compounds. The host crystal is doped with a transition metal laser ion, e.g., chromium, cobalt or iron. In particular, Cr.sup.2+ -doped ZnS and ZnSe generate laser action near 2.3 .mu.m. Oxide, chloride, fluoride, bromide and iodide crystals with similar structures can also be used. Important aspects of these laser materials are the tetrahedral site symmetry of the host crystal, low excited state absorption losses and high luminescence efficiency, and the d.sup.4 and d.sup.6 electronic configurations of the transition metal ions. The same materials are also useful as saturable absorbers for passive Q-switching applications. The laser materials can be used as gain media in amplifiers and oscillators; these gain media can be incorporated into waveguides and semiconductor lasers.

A new class of solid state laser crystals and lasers are formed of transition metaldoped sulfide, selenide, and telluride host crystals which have four fold coordinated substitutional sites. The host crystals include II-VI compounds. The host crystal is doped with a transition metal laser ion, e.g., chromium, cobalt or iron. In particular, Cr{sup 2+}-doped ZnS and ZnSe generate laser action near 2.3 {micro}m. Oxide, chloride, fluoride, bromide and iodide crystals with similar structures can also be used. Important aspects of these laser materials are the tetrahedral site symmetry of the host crystal, low excited state absorption losses and high luminescence efficiency, and the d{sup 4} and d{sup 6} electronic configurations of the transition metal ions. The same materials are also useful as saturable absorbers for passive Q-switching applications. The laser materials can be used as gain media in amplifiers and oscillators; these gain media can be incorporated into waveguides and semiconductor lasers. 18 figs.

We show that, in addition to its thermodynamic properties that make it a good candidate for hydrogen storage, the MgH2 hydride exhibits interesting magnetic properties when doped with some transition metals (TM). Using the Korringa-Kohn-Rostoker method (KKR) combined with the coherent potential approximation in the framework of first-principle calculations, we study the half-metallic ferromagnetic properties of the MgH2 doped with TM: Co, V, Cr, Ti; Mg0.95TM0.05H2. The ferromagnetic state energy is computed and compared with the disordered local moment state energy. We show, from the electronic structure, that doping MgH2 with TM elements can convert the material to a half-metallic with a high wide impurity band and high magnetic moment. We have found that the corresponding Curie temperature is bigger than the room temperature, which is considered as a relevant parameter for spintronic applications. Moreover, the mechanism of the hybridization and the interaction between the magnetic ions are also investigated showing that the double exchange is the underlying mechanism responsible for the magnetism of such materials.

We have investigated the structural, electronic and magnetic properties of hole-doped nitrogenated honey graphene by first-principles calculations. Remarkably, there exists a stable half-metallic ferromagnetism phase with the average spin magnetic moment per carrier of near 1.0 μB in this monolayer system as the carrier density increases from 0 to 1.5 ×1014 cm-2. With further increase of carrier density, the half-metal state vanishes, while the magnetic state remains until the carrier density reaches 4.5 ×1014 cm-2. Our analysis reveals that the predicted itinerant magnetism arises from an exchange splitting of the electronic states at the top of the valence band, where the density of states shows a van Hove singularity. In addition, we have also studied the electron-doped nitrogenated honey graphene, and find the magnetic features are similar to those of the hole-doped system. As synthesis of monolayer nitrogenated honey graphene was reported, half-metallicity of nitrogenated honey graphene are feasible.

Graphical abstract: - Highlights: • Dopant species and dopant/Mn molar ratio affect the shape of Mn{sub 3}O{sub 4} microcrystal. • For Cu and Ni doped Mn{sub 3}O{sub 4}, the spontaneous valence changes of dopant taken place. • An apparent change in the energy bandgap of Mn{sub 3}O{sub 4} with the metaldoping. - Abstract: Synthesis of undoped and transition metal ion doped Mn{sub 3}O{sub 4} microcrystals were achieved through a simple hydrothermal route. The morphologies and structures of the obtained products were characterized using X-ray diffraction, X-ray photoemission spectroscopy and scanning electron microscopy. Results revealed that the low volume percentage of ethanol in the precursor solution limited formation of Mn{sup 2+}, while the introduction of doping ions into the precursor solution caused a direct synthesis of single phase Mn{sub 3}O{sub 4} crystals. For Cu and Ni doping ions, the spontaneous valence changes during the doping process were taken place. The possible doping mechanisms for the formation of single-phase Mn{sub 3}O{sub 4} were discussed briefly. UV–vis spectroscopic studies showed an apparent change in the energy bandgap of Mn{sub 3}O{sub 4} with the metaldoping.

We report that a ferroelectric-like metallic state with reduced anisotropy of polarization is created by the doping of conduction electrons into BaTiO3, on the bases of x-ray/electron diffraction and infrared spectroscopic experiments. The crystal structure is heterogeneous in nanometer-scale, as enabled by the reduced polarization anisotropy. The enhanced infrared intensity of soft phonon along with the resistivity reduction suggests the presence of unusual electron-phonon coupling, which may be responsible for the emergent ferroelectric structure compatible with metallic state. PMID:26289749

The local metallicities of Hf0.97Gd0.03O2, Ga0.97Gd0.03N, Eu0.97Gd0.04O and EuO films were studied through a comparison of the findings from constant initial state spectroscopy using synchrotron light. Resonant enhancements, corresponding to the 4d → 4f transitions of Eu and Gd, were observed in some of the valence band photoemission features. The resonant photoemission intensity enhancements for the Gd 4f photoemission features are far stronger for the more insulating host systems than for the metallic system Eu0.96Gd0.04O. The evidence seems to suggest a correlation between the effective screening in the films and the resonant photoemission process.

An embodiment of the invention combines the superior performance of a polyvinylidene difluoride (PVDF) or polyethyleneoxide (POE) binder, the strong binding force of a styrene-butadiene (SBR) binder, and a source of lithium ions in the form of solid lithium metal powder (SLMP) to form an electrode system that has improved performance as compared to PVDF/SBR binder based electrodes. This invention will provide a new way to achieve improved results at a much reduced cost.

We report a systematic nuclear magnetic resonance investigation of the 23Na spin-lattice relaxation rate, 1/T1, in sodium loaded low-silica X (LSX) zeolite, Nan/Na12-LSX, for various loading levels of sodium atoms n across the metal-to-insulator crossover. For high loading levels of n ≥ 14.2, 1/T1T shows nearly temperature-independent behaviour between 10 K and 25 K consistent with the Korringa relaxation mechanism and the metallic ground state. As the loading levels decrease below n ≤ 11.6, the extracted density of states (DOS) at the Fermi level sharply decreases, although a residual DOS at Fermi level is still observed even in the samples that lack the metallic Drude-peak in the optical reflectance. The observed crossover is a result of a complex loading-level dependence of electric potential felt by the electrons confined to zeolite cages, where the electronic correlations and disorder both play an important role. PMID:26725368

We report a systematic nuclear magnetic resonance investigation of the 23Na spin-lattice relaxation rate, 1/T1, in sodium loaded low-silica X (LSX) zeolite, Nan/Na12-LSX, for various loading levels of sodium atoms n across the metal-to-insulator crossover. For high loading levels of n ≥ 14.2, 1/T1T shows nearly temperature-independent behaviour between 10 K and 25 K consistent with the Korringa relaxation mechanism and the metallic ground state. As the loading levels decrease below n ≤ 11.6, the extracted density of states (DOS) at the Fermi level sharply decreases, although a residual DOS at Fermi level is still observed even in the samples that lack the metallic Drude-peak in the optical reflectance. The observed crossover is a result of a complex loading-level dependence of electric potential felt by the electrons confined to zeolite cages, where the electronic correlations and disorder both play an important role.

One-dimensional porous metallic nanomaterials have attracted much attention due to their unique shape and hollow structure. Herein, the gold nanorods in a porous shell of an AuAg alloy are synthesized via a dealloying process of the core-shell Au@AuAg nanorods at room temperature. The formation of tiny pores in the shell results in the huge red-shift, sharp decrease and drastic broadening of longitudinal surface plasmon resonance absorption. The continuous removal of silver from the porous nanorods leads to the breakage of tiny pores and leaves a rough surface on the nanorods behind. The rough surface gradually becomes smooth in the subsequent dealloying process. The surface structures of these intermediates are correlated with their absorption spectra and catalytic activities for the catalytic reduction of p-nitrophenol. The porous nanorods show a higher catalytic efficiency than the gold nanorods, the core-shell nanorods and the rough nanorods. The results indicate that the dealloying of anisotropic bimetal nanomaterials not only provides an effective pathway to carve the structures on the nanoscale but also offers numerous opportunities to observe novel optical properties and enhanced catalysis performances.One-dimensional porous metallic nanomaterials have attracted much attention due to their unique shape and hollow structure. Herein, the gold nanorods in a porous shell of an AuAg alloy are synthesized via a dealloying process of the core-shell Au@AuAg nanorods at room temperature. The formation of tiny pores in the shell results in the huge red-shift, sharp decrease and drastic broadening of longitudinal surface plasmon resonance absorption. The continuous removal of silver from the porous nanorods leads to the breakage of tiny pores and leaves a rough surface on the nanorods behind. The rough surface gradually becomes smooth in the subsequent dealloying process. The surface structures of these intermediates are correlated with their absorption spectra and

We report accurate energetics of defects introduced in GaN on doping with divalent metals, focusing on the technologically important case of Mg doping, using a model that takes into consideration both the effect of hole localization and dipolar polarization of the host material, and includes a well-defined reference level. Defect formation and ionization energies show that divalent dopants are counterbalanced in GaN by nitrogen vacancies and not by holes, which explains both the difficulty in achieving p-type conductivity in GaN and the associated major spectroscopic features, including the ubiquitous 3.46 eV photoluminescence line, a characteristic of all lightly divalent-metal-doped GaN materials that has also been shown to occur in pure GaN samples. Our results give a comprehensive explanation for the observed behavior of GaN doped with low concentrations of divalent metals in good agreement with relevant experiment.

Nitrogen-doped hollow mesoporous carbon spheres has been synthesized from mesoporous silica spheres using glycine as carbon and nitrogen precursor. The wall of the spheres is composed by broken graphene. The metal free nitrogen-doped hollow mesoporous carbon spheres are proven to be active electrocatalyst for the oxygen reduction reaction in alkaline solution. A unique advantage of the nitrogen-doped hollow mesoporous carbon sphere is its methanol-tolerant property because of the absence of active metal. The catalytic activity is ascribed to the pyridinic-nitrogen formed during pyrolysis and the graphene-like structure. To the best of our knowledge this is the first report on the nitrogen-doped hollow mesoporous carbon sphere as a metal-free electrocatalyst for the oxygen reduction reaction which is an important reaction in fuel cell. The prepared mesoporous carbon material can also be used as catalyst support and find application both in the anode and cathode of fuel cell.

In this viewpoint we discuss the early work of Murphy et al. on the colloidal synthesis of silver nanorods and nanowires, which represents a milestone in the controllable synthesis of anisotropic metal nanoparticles. We present here an overview of the impact of this pioneering work on the later drastic development of solution phase synthesis of shape-controlled metal nanostructures.

Nanostructured metal-contained catalysts are one of the most widely used types of catalysts applied to facilitate some of sluggish electrochemical reactions. However, the high activity of these catalysts cannot be sustained over a variety of pH ranges. In an effort to develop highly active and stable metal-contained catalysts, various approaches have been pursued with an emphasis on metal particle size reduction and doping on carbon-based supports. These techniques enhances the metal-support interactions, originating from the chemical bonding effect between the metal dopants and carbon support and the associated interface, as well as the charge transfer between the atomic metal species and carbon framework. This provides an opportunity to tune the well-defined metal active centers and optimize their activity, selectivity and stability of this type of (electro)catalyst. Herein, recent advances in synthesis strategies, characterization and catalytic performance of single atom metal dopants on carbon-based nanomaterials are highlighted with attempts to understand the electronic structure and spatial arrangement of individual atoms as well as their interaction with the supports. Applications of these new materials in a wide range of potential electrocatalytic processes in renewable energy conversion systems are also discussed with emphasis on future directions in this active field of research.

We investigate the Capacitance-Voltage (CV) measurement to study the electrically active boron doping in Si nanocrystals (ncSi) embedded in SiO2. The ncSi thin films with high resistivity (200-400 Ω cm) can be measured by using an inverted metal oxide semiconductor (MOS) structure (Al/ncSi (B)/SiO2/Si). This device structure eliminates the complications from the effects of lateral current flow and the high sheet resistance in standard lateral MOS structures. The characteristic MOS CV curves observed are consistent with the effective p-type doping. The CV modeling method is presented and used to evaluate the electrically active doping concentration. We find that the highly boron doped ncSi films have electrically active doping of 1018-1019 cm-3 despite their high resistivity. The saturation of doping at about 1.4 × 1019 cm-3 and the low doping efficiency less than 5% are observed and discussed. The calculated effective mobility is in the order of 10-3 cm2/V s, indicating strong impurity/defect scattering effect that hinders carriers transport.

We investigate the Capacitance-Voltage (CV) measurement to study the electrically active boron doping in Si nanocrystals (ncSi) embedded in SiO{sub 2}. The ncSi thin films with high resistivity (200–400 Ω cm) can be measured by using an inverted metal oxide semiconductor (MOS) structure (Al/ncSi (B)/SiO{sub 2}/Si). This device structure eliminates the complications from the effects of lateral current flow and the high sheet resistance in standard lateral MOS structures. The characteristic MOS CV curves observed are consistent with the effective p-type doping. The CV modeling method is presented and used to evaluate the electrically active doping concentration. We find that the highly boron doped ncSi films have electrically active doping of 10{sup 18}–10{sup 19 }cm{sup −3} despite their high resistivity. The saturation of doping at about 1.4 × 10{sup 19 }cm{sup −3} and the low doping efficiency less than 5% are observed and discussed. The calculated effective mobility is in the order of 10{sup −3} cm{sup 2}/V s, indicating strong impurity/defect scattering effect that hinders carriers transport.

As noble metal nanoparticles are deployed into increasingly sophisticated environments, it is necessary to fully develop our understanding of nanoparticle behavior and the corresponding instrument responses. In this paper, we report on the optical response of three important gold nanorod configurations under dark field and differential interference contrast (DIC) microscopy after first establishing their absolute geometries with transmission electron microscopy (TEM). The observed longitudinal plasmon wavelengths of single nanorods are located at wavelengths consistent with previously developed theory. A dimer is shown exhibiting a multipole plasmon at wavelengths that are consistent with the dipole plasmon of single nanorods in the sample. DIC can also distinguish a single nanorod from a pair of uncoupled nanorods with an interparticle distance below the diffraction limit. The experimental observations are consistent with simulated DIC images using a DIC point spread function. The findings herein are a critical step toward being able to characterize nanorods in dynamic environments without the use of electron microscopy.

With a view to investigate the structural, electronic and magnetic properties of Ni (5%) doped SnO2 diluted magnetic semiconductor nanorods prepared by a PEG-6000 assisted wet chemical route, a systematic investigation has been carried out. The micro structural properties were investigated by Rietveld refinement of XRD data, AFM, TEM, EDS, SAED, FTIR, Raman scattering and XPS measurements. These studies revealed that Sn0.95Ni0.05O2 nanorods have a polycrystalline single phase tetragonal rutile structure without any detectable impurity phases and the aspect ratios of the nanorods are in the range 2.85-10.2. The deconvoluted XPS core level Ni 2p spectral studies determined the oxidation state of Ni as +2. The nanosize effects and local defects are found to influence the local electronic structure of materials. From M-H, M-T, m agnetic force microscopy (MFM) and ESR studies, all the samples are found to exhibit clear room temperature ferromagnetism without any metallic clusters. The magnetization behaviour is found to depend on the overlap of percolated bound magnetic polarons and their interactions with dopant induced defects. The magnetic exchange interactions are found to depend on the aggregation behaviour of nanorods, exchange media, the surface diffusion behaviour of randomly distributed Ni ions and the modification of electronic structure.

We found a linear relationship between the metal-insulator transition (MIT) temperature and the A(+) ionic radius of the beta-A(0.33)V(2)O(5) bronze family, leading our attention to beta-K(0.33)V(2)O(5) which has been neglected for a long time. We have introduced a facile hydrothermal method to obtain the single-crystalline beta-K(0.33)V(2)O(5) nanorods. As expected, both the temperature-dependence of the resistivity and magnetization demonstrated MITs at about 72 K for beta-K(0.33)V(2)O(5), thus matching well with the linear relationship described above. The beta-K(0.33)V(2)O(5) was assigned as a new member of the beta-A(0.33)V(2)O(5) bronze family for their similar crystal and electronic structures and their MIT property; this addition enriches the beta-A(0.33)V(2)O(5) bronze family.

We investigate the limiting electrical conductivity of BiFeO3 (BFO) nanofibers via first-principles modelling and experiments. Based on a semi-empirical approach, all transition metals are first screened for their suitability to form an acceptor in BFO. The resultant candidates (e.g., Ni, Cu and Ag) are further studied by more sophisticated electronic structure theory and experiments. Accordingly, a systematic approach in forecasting the electrical conduction in BFO nanofibers is established. The calculated results show that Ag(+) cations prefer substitutions of Bi(3+) while Ni(2+) and Cu(2+) prefer substitution of Fe(3+) sites to form acceptors. All three metals contribute to an increased overall hole concentration which may lead to a conductivity limit in BFO. These predictions were confirmed consistently through the synthesis and electrical testing of Ni-, Cu- and Ag-doped BFO nanofibers. Finally, our results indicate that the conductivity limit is approached by Ni doping in BFO. The methodology presented here may be extended to search for the doping conductivity limits of other semiconductors of interest.

New bone chars for fluoride adsorption from drinking water have been synthetized via metallicdoping using aluminum and iron salts. A detailed statistical analysis of the metaldoping process using the signal-to-noise ratios from Taguchi's experimental designs and its impact on the fluoride adsorption properties of modified bone chars have been performed. The best conditions, including the proper metallic salt, for metaldoping were identified to improve the fluoride uptakes of modified bone chars. Results showed that the fluoride adsorption properties of bone chars can be enhanced up to 600% using aluminum sulfate for the surface modification. This aluminum-based adsorbent showed an adsorption capacity of 31 mg/g, which outperformed the fluoride uptakes reported for several adsorbents. Surface interactions involved in the defluoridation process were established using FTIR, DRX and XPS analysis. Defluoridation using the metal-doped bone chars occurred via an ion exchange process between fluoride ions and the hydroxyl groups on the adsorbent surface, whereas the Al(OH)xFy, FexFy, and CaF2 interactions could play also an important role in the removal process. These metal-doped adsorbents anticipate a promising behavior in water treatment, especially in developing countries where the efficiency - cost tradeoff is crucial for implementing new defluoridation technologies.

ZnS and metal (Mn, Cu)-doped-ZnS were successfully prepared by wet chemical synthetic route. The understanding of substituted metal ions (Mn, Cu) into ZnS leads to transfer the luminescent centre by small amount of metal dopant (Mn, Cu). Fourier transform infrared and X-ray diffraction were used to determine chemical bonding and crystal structure, respectively. It showed that small amount of metal (Mn, Cu) can be completely substituted into ZnS lattice. X-ray fluorescence was used to confirm the existence of metal-doped ZnS. Scanning electron microscope revealed that their particles exhibits blocky particle with irregular sharp. Laser confocal microscope and photoluminescence spectroscopy showed that ZnS and metal-doped-ZnS exhibited intense, stable, and tunable emission covering the blue to red end of the visible spectrum. ZnS, Mn-doped-ZnS and Cu-doped-ZnS generated blue, yellow and green color, respectively.

A new numerical simulation method using the finite element methodology (FEM) is presented to study electromagnetic scattering due to an arbitrarily shaped material body doped randomly with thin and short metallic wires. The FEM approach described in many standard text books is appropriately modified to account for the presence of thin and short metallic wires distributed randomly inside an arbitrarily shaped material body. Using this modified FEM approach, the electromagnetic scattering due to cylindrical, spherical material body doped randomly with thin metallic wires is studied.

Multi-non-metal-doped TiO{sub 2} nanotubes were fabricated by electrochemical anodization of Ti in the mixed acid electrolyte of C{sub 2}H{sub 2}O{sub 4}.2H{sub 2}O and HIO{sub 3} containing NH{sub 4}F. The samples were annealed in air and characterized by FE-SEM, XRD, XPS and DRS. The results indicate non-metals of N, F and I are successfully doped into TiO{sub 2} nanotubes in aqueous solution by adjusting the electrolyte composition. The multi-non-metal-doped samples display a significant visible-light response. Additionally, the atomic concentration of non-metals is closely related with the electrolyte composition.

The ability to form reliable, low-resistance Ohmic contacts is of critical importance to the ongoing development of oxide electronics. Most metals form Schottky barriers when deposited on oxide surfaces. Ohmic contacts rarely occur, and the associated contact resistances are not particularly low. Little is known at an atomistic level about what leads to a good Ohmic contact on a wide-gap oxide. Here we describe the structure of a simple, yet exceptionally low-contact resistance Ohmic metal on an important oxide semiconductor -- epitaxial Cr on Nb-doped SrTiO3(001). Heteroepitaxial growth is accompanied by Cr diffusion into the STO and occupation of interstitial sites within the first few atomic planes. Interstitial Cr is ionized and the resulting electrons occupy the STO conduction band, resulting in effective metallization near the interface.

Creating highly electrically conducting cables from macroscopic aggregates of carbon nanotubes, to replace metallic wires, is still a dream. Here we report the fabrication of iodine-doped, double-walled nanotube cables having electrical resistivity reaching ~10-7 Ω.m. Due to the low density, their specific conductivity (conductivity/weight) is higher than copper and aluminum and is only just below that of the highest specific conductivity metal, sodium. The cables exhibit high current-carrying capacity of 104~105 A/cm2 and can be joined together into arbitrary length and diameter, without degradation of their electrical properties. The application of such nanotube cables is demonstrated by partly replacing metal wires in a household light bulb circuit. The conductivity variation as a function of temperature for the cables is five times smaller than that for copper. The high conductivity nanotube cables could find a range of applications, from low dimensional interconnects to transmission lines.

We present a combined experimental and theoretical study of memristive switching in a self-assembled mesh of ZnO nanorods. A ZnO nanorod mesh spans the area between Ag contacts in a device that exhibits hysteresis with large ON/OFF ratio, reaching ION/IOFF values of 104. We show that switching behavior depends critically on the geometry of the nanorod mesh. We employ density functional theory (DFT) calculations to deduce the mechanism for resistive switching for the nanorod mesh. Redistribution of Ag atoms, driven by an electrical field, leads to the formation and evolution of a conducting path through nanorods. Field-induced migration of Ag atoms changes the doping level of nanorods and modulates their conductivity. Using static DFT and nudged-elastic-band calculations, we investigate the energy of interaction between Ag clusters and a ZnO surface, including migration barriers of Ag atoms. Current-voltage (I-V) characteristics are modeled using percolation theory in a nanorod mesh. To describe the dynamics of SET/RESET phenomena, model parameters include the experimentally observed nanorod geometry and the energetics of Ag on ZnO surfaces, obtained from DFT calculations. This work was supported by NSF Grant DMR-1207241, DOE Grant DE-FG02-09ER46554, and the McMinn Endowment at Vanderbilt University. Computational support was provided by the NSF XSEDE under Grant #DMR TG-DMR130121.

First-principles calculations within the density functional theory (DFT) have been carried out to study hydrogen molecules dissociation and diffusion on clean and transition metals (TMs) doped Mg(0 0 0 1) surfaces following Pozzo et al. work. Firstly, the stability of Mg(0 0 0 1) surface doped with transition metals atom has been studied. The results showed that transition metals on the left of the table tend to substitute Mg in the second layer, while the other transition metals prefer to substitute Mg in the first layer. Secondly, we studied hydrogen molecules dissociation and diffusion on clean and Mg(0 0 0 1) surfaces which the transition metal atoms substituted both in the first layer and second layer. When transition metal atoms substitute in the first layer, the results agree with the Pozzo et al. result; when transition metal atoms substitute in the second layer, the results showed that the transition metals on the left of the periodic table impact on the dissociation barriers is less. However, for the transition metals (Mn, Fe, Co, Ni) on the right, there is a great impact on the barriers. The transition metalsdoped surfaces bind the dissociated H atoms loosely, making them easily diffused. The results further reveal that the Fe dopant on the Mg surface is the best choice for H2 dissociation and hydrogen storage.

Elongated noble-metal nanoparticles and methods for their manufacture are disclosed. The method involves the formation of a plurality of elongated noble-metal nanoparticles by electrochemical deposition of the noble metal on a high surface area carbon support, such as carbon nanoparticles. Prior to electrochemical deposition, the carbon support may be functionalized by oxidation, thus making the manufacturing process simple and cost-effective. The generated elongated nanoparticles are covalently bound to the carbon support and can be used directly in electrocatalysis. The process provides elongated noble-metal nanoparticles with high catalytic activities and improved durability in combination with high catalyst utilization since the nanoparticles are deposited and covalently bound to the carbon support in their final position and will not change in forming an electrode assembly.

The enhancement of catalytic performance of cobalt phosphide-based catalysts for the hydrogen evolution reaction (HER) is still challenging. In this work, the doping effect of some transition metal (M = Fe, Ni, Cu) on the electrocatalytic performance of the M-Co2P/NCNTs (NCNTs, nitrogen-doped carbon nanotubes) hybrid catalysts for the HER was studied systematically. The M-Co2P/NCNTs hybrid catalysts were synthesized via a simple in situ thermal decomposition process. A series of techniques, including X-ray diffraction, X-ray photoelectron spectroscopy, inductively coupled plasma-optical emission spectrometry, transmission electron microscopy, and N2 sorption were used to characterize the as-synthesized M-Co2P/NCNTs hybrid catalysts. Electrochemical measurements showed the catalytic performance according to the following order of Fe-Co2P/NCNTs > Ni-Co2P/NCNTs > Cu-Co2P/NCNTs, which can be ascribed to the difference of structure, morphology, and electronic property after doping. The doping of Fe atoms promote the growth of the [111] crystal plane, resulting in a large specific area and exposing more catalytic active sites. Meanwhile, the Fe(δ+) has the highest positive charge among all the M-Co2P/NCNTs hybrid catalysts after doping. All these changes can be used to contribute the highest electrocatalytic activity of the Fe-Co2P/NCNTs hybrid catalyst for HER. Furthermore, an optimal HER electrocatalytic activity was obtained by adjusting the doping ratio of Fe atoms. Our current research indicates that the doping of metal is also an important strategy to improve the electrocatalytic activity for the HER.

Doped TiO(2) semiconductor powders were synthesized using Al and W as photovoltaic property-enhancing impurities. Al-doped TiO(2) electrodes increased open-circuit voltage (V(oc)), but reduced short-circuit current (I(sc)). In contrast, W-doped TiO(2) had an opposite effect. However, dye-sensitized solar cell efficiency fabricated with doped TiO(2) was remarkably better than that of undoped TiO(2). It seems that these phenomena were related to electrical surface-state modifications induced by metal-ion dopants. These modifications led to significant changes in powder aggregation, charge transfer kinetics, and dye adsorption characteristics. The highest efficiency was found by using (Al+W)-doped TiO(2) nanopowders.

Roll-to-roll manufacturing of CdTe solar cells on flexible metal foil substrates is one of the most attractive options for low-cost photovoltaic module production. However, various efforts to grow CdTe solar cells on metal foil have resulted in low efficiencies. This is caused by the fact that the conventional device structure must be inverted, which imposes severe restrictions on device processing and consequently limits the electronic quality of the CdTe layer. Here we introduce an innovative concept for the controlled doping of the CdTe layer in the inverted device structure by means of evaporation of sub-monolayer amounts of Cu and subsequent annealing, which enables breakthrough efficiencies up to 13.6%. For the first time, CdTe solar cells on metal foil exceed the 10% efficiency threshold for industrialization. The controlled doping of CdTe with Cu leads to increased hole density, enhanced carrier lifetime and improved carrier collection in the solar cell. Our results offer new research directions for solving persistent challenges of CdTe photovoltaics.

Two different types of Ru metaldoped TiO2 nanoparticles were synthesized using a sole gel method with and without ionic liquid. It was clearly observed during characterizing the Ru-TiO2-IL catalyst with respect to Ru-TiO2 catalyst that Ru metal is dispersed while using ionic liquid as reaction medium for catalyst synthesis. TEM image also reveals the presence of agglomeration free, stable and well dispersed Ru metaldoped TiO2 nanoparticles in Ru-TiO2-IL over a Ru-TiO2 catalyst. Such unique feature of the Ru-TiO2-IL catalyst reflected in terms of high TON /TOF value of formic acid during the hydrogenation reaction of CO2 in task specific ionic liquid medium. Low catalysts loading, moisture/air stability, high selectivity, an easy reaction protocol for catalyst synthesis as well as stress-free reaction condition along with 6 times catalysts recycling is the major outcomes of the proposed protocol.

Alkali and alkali-earth metal hydrides have high volumetric and gravimetric hydrogen densities, but due to their high thermodynamic stability, they possess high dehydrogenation temperatures which may be reduced by transforming these compounds into less stable states/configurations. We present a systematic computational study of the electron doping effects on the stability of the alkali metal hydride NaH substituted with Mg, using the self-consistent version of the virtual crystal approximation to model the alloy Na1‑x Mg x H. The phonon dispersions were studied paying special attention to the crystal stability and the correlations with the electronic structure taking into account the zero point energy contribution. We found that substitution of Na by Mg in the hydride invokes a reduction of the frequencies, leading to dynamical instabilities for Mg content of 25%. The microscopic origin of these instabilities could be related to the formation of ellipsoidal Fermi surfaces centered at the L point due to the metallization of the hydride by the Mg substitution. Applying the quasiharmonic approximation, thermodynamic properties like heat capacities, vibrational entropies and vibrational free energies as a function of temperature at zero pressure are obtained. These properties determine an upper temperature for the thermodynamic stability of the hydride, which decreases from 600 K for NaH to 300 K at 20% Mg concentration. This significant reduction of the stability range indicates that dehydrogenation could be favoured by electron doping of NaH.

The metal-like behaviors and metal-semiconductor transition (MST) of highly conducting Zn1- x Al x O ( x = 1 at.% to 10 at.%) thin films deposited by cosputtering on a-Al2O3 have been investigated. The temperature-dependent transport properties reveal that the Zn1- x Al x O films were highly degenerate. The MST temperature ( T MST) varied from 190 K to 260 K with Al doping from x = 2 at.% to 10 at.%. A simple degenerate band model is used to explain the observed shift in the metal-like behaviors upon Al doping. An empirical approach is used to analyze the resistivity functional below TMST, taking into account the contributions from both the weak localization and Coulomb interactions in explaining the MST. Analysis by least-square fittings of measured data shows excellent agreement. The optical bandgap increases with carrier concentration as n Hall 2/3 , which is interpreted as the Burstein-Moss shift for a nonparabolic effective mass. Such nonparabolicity is scrutinized by quantitative comparisons of the plasma edge values n optical versus the n Hall values.

The metal-like behaviors and metal-semiconductor transition (MST) of highly conducting Zn1-x Al x O (x = 1 at.% to 10 at.%) thin films deposited by cosputtering on a-Al2O3 have been investigated. The temperature-dependent transport properties reveal that the Zn1-x Al x O films were highly degenerate. The MST temperature (T MST) varied from 190 K to 260 K with Al doping from x = 2 at.% to 10 at.%. A simple degenerate band model is used to explain the observed shift in the metal-like behaviors upon Al doping. An empirical approach is used to analyze the resistivity functional below TMST, taking into account the contributions from both the weak localization and Coulomb interactions in explaining the MST. Analysis by least-square fittings of measured data shows excellent agreement. The optical bandgap increases with carrier concentration as n {Hall/2/3}, which is interpreted as the Burstein-Moss shift for a nonparabolic effective mass. Such nonparabolicity is scrutinized by quantitative comparisons of the plasma edge values n optical versus the n Hall values.

Roll-to-roll manufacturing of CdTe solar cells on flexible metal foil substrates is one of the most attractive options for low-cost photovoltaic module production. However, various efforts to grow CdTe solar cells on metal foil have resulted in low efficiencies. This is caused by the fact that the conventional device structure must be inverted, which imposes severe restrictions on device processing and consequently limits the electronic quality of the CdTe layer. Here we introduce an innovative concept for the controlled doping of the CdTe layer in the inverted device structure by means of evaporation of sub-monolayer amounts of Cu and subsequent annealing, which enables breakthrough efficiencies up to 13.6%. For the first time, CdTe solar cells on metal foil exceed the 10% efficiency threshold for industrialization. The controlled doping of CdTe with Cu leads to increased hole density, enhanced carrier lifetime and improved carrier collection in the solar cell. Our results offer new research directions for solving persistent challenges of CdTe photovoltaics.

Alkali and alkali-earth metal hydrides have high volumetric and gravimetric hydrogen densities, but due to their high thermodynamic stability, they possess high dehydrogenation temperatures which may be reduced by transforming these compounds into less stable states/configurations. We present a systematic computational study of the electron doping effects on the stability of the alkali metal hydride NaH substituted with Mg, using the self-consistent version of the virtual crystal approximation to model the alloy Na1-x Mg x H. The phonon dispersions were studied paying special attention to the crystal stability and the correlations with the electronic structure taking into account the zero point energy contribution. We found that substitution of Na by Mg in the hydride invokes a reduction of the frequencies, leading to dynamical instabilities for Mg content of 25%. The microscopic origin of these instabilities could be related to the formation of ellipsoidal Fermi surfaces centered at the L point due to the metallization of the hydride by the Mg substitution. Applying the quasiharmonic approximation, thermodynamic properties like heat capacities, vibrational entropies and vibrational free energies as a function of temperature at zero pressure are obtained. These properties determine an upper temperature for the thermodynamic stability of the hydride, which decreases from 600 K for NaH to 300 K at 20% Mg concentration. This significant reduction of the stability range indicates that dehydrogenation could be favoured by electron doping of NaH.

Two-dimensional transition-metal dichalcogenides (2D TMDs) have attracted much attention recently due to potential applications including optoelectronic devices. Atomically thin layers of materials such as MoS2, WS2, NbS2, NbSe2, TaTe2 can easily be synthesized by exfoliation techniques and exhibit variety electronic phases such as metal, semiconductor, superconductor depending on the choice of metal. Most of the TMDs are nonmagnetic and various techniques have been proposed to induce or modulate magnetic properties that are essential for nanoelectronic device applications. We use DFT calculations to analyze the effect of strain, hydrogen adsorption, and doping. Emphasis is on the magnetic properties of NbSe2 monolayers containing vacancies and 3 d transition metal atoms. We find that magnetism can be induced by vacancy creation and transition metal-substitution in NbSe2, with effects similar to strain and hydrogen adsorption. The moment mainly arises from the localized nonbonding 3d electrons of the transition-metal atoms. Our findings contribute to the ongoing search ``for-better-than-graphene'' thin-film materials for novel electronic devices. This research is partially supported by DOE BES (DE-FG02-04ER46152).

Rare-earth-doped magnetic-optic bifunctional alkaline-earth metal fluoride nanocrystals have been successfully synthesized via a facile microwave-assisted process. The as-prepared nanocrystals were monodisperse and could form stable colloidal solutions in polar solvents, such as water and ethanol. They show bright-green fluorescence emisson. Furthermore, Gd(3+)-doped ones exhibit paramagnetic behavior at room temperature and superparamagnetic behavior at 2 K.

Charge carrier recombination and durability issues are major problems in photocatalytic hydrogen (H2) evolution processes. Thus, there is a very important necessitate to extend an efficient photocatalyst to control charge-carrier dynamics in the photocatalytic system. We have developed copper molybdenum sulfide (Cu2MoS4) nanosheets as co-catalysts with CdS nanorods for controlling charge carriers without recombination for use in photocatalytic H2 evolution under simulated solar light irradiation. Effective control and utilization of charge carriers are possible by loading Cu2MoS4 nanosheets onto the CdS nanorods. The loading compensates for the restrictions of CdS, and stimulated synergistic effects, such as efficient photoexcited charge separation, lead to an improvement in photostability because of the layered structure of the Cu2MoS4nanosheets. These layered Cu2MoS4 nanosheets have emerged as novel and active replacements for precious noble metal co-catalysts in photocatalytic H2 production by water splitting. We have obtained superior H2 production rates by using Cu2MoS4 loaded CdS nanorods. The physicochemical properties of the composites are analyzed by diverse characterization techniques.

A powerful low-cost electrocatalyst, nanorod Nb2O5, is synthesized using the hydrothermal method with monoclinic phases and simultaneously deposited on the surface of a graphite felt (GF) electrode in an all vanadium flow battery (VRB). Cyclic voltammetry (CV) study confirmed that Nb2O5 has catalytic effects toward redox couples of V(II)/V(III) at the negative side and V(IV)/V(V) at the positive side to facilitate the electrochemical kinetics of the vanadium redox reactions. Because of poor conductivity of Nb2O5, the performance of the Nb2O5 loaded electrodes is strongly dependent on the nanosize and uniform distribution of catalysts on GF surfaces. Accordingly, an optimal amount of W-doped Nb2O5 nanorods with minimum agglomeration and improved distribution on GF surfaces are established by adding water-soluble compounds containing tungsten (W) into the precursor solutions. The corresponding energy efficiency is enhanced by ∼10.7% at high current density (150 mA·cm(-2)) as compared with one without catalysts. Flow battery cyclic performance also demonstrates the excellent stability of the as prepared Nb2O5 catalyst enhanced electrode. These results suggest that Nb2O5-based nanorods, replacing expensive noble metals, uniformly decorating GFs holds great promise as high-performance electrodes for VRB applications.

We perform a thorough study of the extended Hubbard model featuring local and nearest-neighbor Coulomb repulsion. Using the dynamical mean-field theory we investigated the zero-temperature phase diagram of this model as a function of the chemical doping. The interplay between local and nonlocal interactions drives a variety of phase transitions connecting two distinct charge-ordered insulators, i.e., half filled and quarter filled, a charge-ordered metal and a Mott-insulating phase. We characterize these transitions and the relative stability of the solutions and we show that the two interactions conspire to stabilize the quarter-filled charge-ordered phase.

To improve photocatalytic activity of a coordination polymer (CP) in the visible light region, five different transition metal ions (Fe(3+), Cr(3+), Ru(3+), Co(2+) and Ni(2+)) were introduced into its framework through an ion-exchange process. Among all the resulting transition metal ion doped coordination polymers (TMI/CPs), the one doped with Fe(3+) took on the most excellent photocatalytic activity and the highest quantum yields in the visible light region, decomposing 94% Rhodamine B (RhB) in 8 hours. It can be attributed to the doping of Fe(3+), which reduced the band gap (Eg) of the original CP, facilitating photocatalysis of the obtained polymer. Compared with the coordination polymer with Fe(3+) as a dopant, products doped with other metal ions presented weaker photocatalytic activities in the visible light region, while under the irradiation of ultraviolet light, they showed favorable photocatalytic properties. The results suggest that to dope transition metal ions into the framework of CPs would be an ideal option for enhancing the photocatalytic activity of coordination polymers.

Using the first-principles calculations based on the density functional theory, we have studied the magnetism and electronic structure of Fe-doped Zinc Phosphide (Zn3P2). Our results show that the half-metallic ground state and ferromagnetic stability for the small Fe concentrations considered in our study. The stability of the doped material has been studied by calculating the heat of formation and analyzing the minimum total energies in nonmagnetic and ferromagnetic phases. A large value of the magnetic moment is obtained from our calculations and our calculation suggests that the Fe-doped Zn3P2 may be a useful material in semiconductor spintronics.

We compare the single-particle plasmonic sensitivity of silver and gold nanorods with similar resonance wavelengths by monitoring the plasmon resonance shift upon changing the environment from water to 12.5% sucrose solution. We find that silver nanoparticles have 1.2 to 2 times higher sensitivity than gold, in good agreement with simulations based on the boundary-elements-method (BEM). To exclude the effect of particle volume on sensitivity, we test gold rods with increasing particle width at a given resonance wavelength. Using the Drude-model of optical properties of metals together with the quasi-static approximation (QSA) for localized surface plasmons, we show that the dominant contribution to higher sensitivity of silver is the lower background polarizability of the d-band electrons and provide a simple formula for the sensitivity. We improve the reversibility of the silver nanorod sensors upon repeated cycles of environmental changes by blocking the high energy parts of the illumination light.

This review summarizes the state-of-the-art in the search for room temperature ferromagnetic semiconductors based on transition-metal- and rare-earth-doped nitrides. The major methods of synthesis are reported, together with an overview of the magnetic, structural, electrical and optical characterization of the materials systems, where available. The controversial experimental results concerning the actual value of the apparent Curie temperature in magnetically doped nitrides are highlighted, the inadequacy of standard characterization methods alone and the necessity of a possibly exhaustive structural investigation of the systems are proven and underlined. Furthermore, the dependence on the fabrication parameters of the magnetic ions incorporation into the semiconductor matrix is discussed, with special attention to the fundamental concepts of solubility limit and spinodal decomposition. It is argued that high-temperature ferromagnetic features in magnetically doped nitrides result from the presence of nanoscale regions containing a high concentration of the magnetic constituents. Various functionalities of these multicomponent systems are listed. Moreover, we give an extensive overview on the properties of single magnetic-impurity states in the nitride host. The understanding of this limit is crucial when considering the most recent suggestions for the control of the magnetic ion distribution—and consequently of the magnetic response—through the Fermi level engineering as well as to indicate roads for achieving high-temperature ferromagnetism in the systems containing a uniform distribution of magnetic ions.

In this paper, glasses based on bismuth, germanium, gallium and sodium oxides have been synthesized in terms of low phonon energy (724 cm-1) and high thermal stability (ΔT = 127°C). Synthesis process have been optimized using low vacuum conditions (approx. 60 mBar) to improve the transmittance in the mid-infrared region and decrease the content of hydroxide groups in the material structure. Glass doped with erbium ions has been pumped with high power diode (λexc = 980 nm) to obtain luminescence in the band of 2.7 μm as a result of Er3+: 4I11/2 -> 4I13/2 radiative transition. For analysis of emission properties and energy transfer mechanisms, glasses co-doped with Er3+/Ho3+, Er3+/Pr3+, Er3+/Nd3+ ions have been synthesized. Obtained results indicated energy transfer phenomenon between lanthanide ions and elements forming the glass matrix. This demonstrates that developed heavy metal oxide glass doped with optimal rare earth elements system is an attractive material for mid-infrared applications.

Aluminum hydride, AlH3, has inherently high gravimetric and volumetric properties for onboard vehiclular hydrogen storage (10 wt% H2 and 0.148 kg H2/L). Yet it has been widely neglected because of its kinetic limitations for low-temperature H2 desorption and the thermodynamic difficulties associated with recharging. This paper considers a scenario whereby doped AlH3 is decomposed onboard and recharged offboard. In particular, we show that particle size control and doping with small levels of alkali metal hydrides (e.g., LiH) results in accelerated H2 desorption rates nearly high enough to supply fuel-cell and ICE vehicles. The mechanism of enhanced H2 desorption is associated with the formation of alanate windows (e.g., LiAlH4) between the AlH3 particles and the external gas phase. These alanate windows can be doped with Ti to further enhance transparency, even to the point of accomplishing slow decomposition of AlH3 at room temperature. It is highly likely 2010 gravimetric and volumetric vehicular system targets (6 wt% H2 and 0.045 kg/L) can be met with AlH3. But a new, low-cost method of offboard regeneration of spent Al back to AlH3 is yet needed.

The boron-doped diamond (BDD) powder consisting of 40-100 μm particles was synthesized at 5 GPa and 1500-1600 °C from a mixture of 50 wt% graphite and 50 wt% Ni-Mn catalyst with an addition of 1 wt% or 5 wt% boron powder. The size of crystal domains of doped and non-doped diamond was evaluated as a coherent scattering region by X-ray diffraction (XRD) and using small-angle neutron scattering (SANS), being ≥180 nm (XRD) and 100 nm (SANS). Magnetic impurities of NiMnx originating from the catalyst in the synthesis, which prevent superconductivity, were detected by magnetization measurements at 2-300 K. X-ray photoelectron spectroscopy, the temperature dependence of the resistivity, XRD, and Raman spectroscopy reveal that the concentration of electrically active boron is as high as (2±1)×1020 cm-3 (0.1 at%). To the best of our knowledge, this is the highest boron content for BDD synthesized in high-pressure high-temperature process with metal catalysts.

In this work, citric acid-capped and ethylene glycol-stabilized pristine and transition metal (TM=Co, Fe, Mn and Ni)-doped ZnO nanoparticles with the generic formula Zn1- x TM x O, x = 0.01 and 0.02, have been synthesized by sol-gel method. XRD confirmed the phase purity of all the samples. Average crystallite size calculated from Scherrer formula was within the range of 43 ± 25 nm for different doped samples. The Raman spectra of (Co, Mn and Ni)-doped ZnO show strong E 2 (high) and E 1 (LO) modes. The synthesized samples also show strong luminescent emission from inherent Zn and O point defects (interstitial and vacancies) along with a sharp excitonic peak centred at 362 nm. Magnetic studies at 300 K reveal that all samples show weak room-temperature ferromagnetism at low magnetic fields with unsaturated M-H plot up to a measuring field of 5 T.

The magnetic properties and electronic structures of pure, doped and defective cerium oxide (CeO2) have been studied theoretically by means of ab initio calculations based on the density function theory (DFT) with the hybrid HF/DFT technique named PBE0. Carbon (C), nitrogen (N), phosphorus (P), sulphur (S), lanthanum (La) and praseodymium (Pr) doped in CeO2 and CeO2 containing oxygen vacancies (Ov) were considered. Our spin-polarized calculations show that C, N, Pr dopants and Ov defects magnetize the non-magnetic CeO2 in different degree. The optical band gap related to photocatalysis for pure CeO2, corresponding to the ultraviolet region, is reduced obviously by C, N, S, Pr impurities and oxygen vacancies, shifting to the visible region and even further to the infrared range. Especially, N-, S- and Pr-doped CeO2 could be used to photocatalytic water splitting for hydrogen production. As the concentration of Ov increasing up to 5%, the CeO2 exhibits a half-metallic properties.

The magnetic properties and electronic structures of pure, doped and defective cerium oxide (CeO2) have been studied theoretically by means of ab initio calculations based on the density function theory (DFT) with the hybrid HF/DFT technique named PBE0. Carbon (C), nitrogen (N), phosphorus (P), sulphur (S), lanthanum (La) and praseodymium (Pr) doped in CeO2 and CeO2 containing oxygen vacancies (Ov) were considered. Our spin-polarized calculations show that C, N, Pr dopants and Ov defects magnetize the non-magnetic CeO2 in different degree. The optical band gap related to photocatalysis for pure CeO2, corresponding to the ultraviolet region, is reduced obviously by C, N, S, Pr impurities and oxygen vacancies, shifting to the visible region and even further to the infrared range. Especially, N-, S- and Pr-doped CeO2 could be used to photocatalytic water splitting for hydrogen production. As the concentration of Ov increasing up to 5%, the CeO2 exhibits a half-metallic properties. PMID:27554285

The magnetic properties and electronic structures of pure, doped and defective cerium oxide (CeO2) have been studied theoretically by means of ab initio calculations based on the density function theory (DFT) with the hybrid HF/DFT technique named PBE0. Carbon (C), nitrogen (N), phosphorus (P), sulphur (S), lanthanum (La) and praseodymium (Pr) doped in CeO2 and CeO2 containing oxygen vacancies (Ov) were considered. Our spin-polarized calculations show that C, N, Pr dopants and Ov defects magnetize the non-magnetic CeO2 in different degree. The optical band gap related to photocatalysis for pure CeO2, corresponding to the ultraviolet region, is reduced obviously by C, N, S, Pr impurities and oxygen vacancies, shifting to the visible region and even further to the infrared range. Especially, N-, S- and Pr-doped CeO2 could be used to photocatalytic water splitting for hydrogen production. As the concentration of Ov increasing up to 5%, the CeO2 exhibits a half-metallic properties.

Metal organic coordination polymers (CPs), as most attractive multifunctional materials, have been studied extensively in many fields. However, metal-biomolecule CPs and CPs' electrochemical properties and applications were studied much less. We focus on this topic aiming at electrochemical biosensors with excellent performance and high biocompatibility. A new nanoscaled metal-biomolecule CP, Mn-tyr, containing manganese and tyrosine, was synthesized hydrothermally and characterized by various techniques, including XRD, TEM, EDS, EDX mapping, elemental analysis, XPS, and IR. Electrode modified with Mn-tyr showed novel bidirectional electrocatalytic ability toward both reduction and oxidation of H2O2, which might be due to Mn. With the assistance of CNTs, the sensing performance of Mn-tyr/CNTs/GCE was improved to a much higher level, with high sensitivity of 543 mA mol(-1) L cm(-2) in linear range of 1.00×10(-6)-1.02×10(-4) mol L(-1), and detection limit of 3.8×10(-7) mol L(-1). Mn-tyr/CNTs/GCE also showed fast response, high selectivity, high steadiness and reproducibility. The excellent performance implies that the metal-biomolecule CPs are promising candidates for using in enzyme-free electrochemical biosensing.

The direct optical monitoring of electron exchange on single plasmonic nanoparticles, involved in chemical reactions with gas molecules, is one of the main challenges in the heterogeneous catalysis and gas sensing fields. Catalysts are substances that speed up reactions by providing an alternative pathway with lower activation energy than that required for the uncatalysed reaction. A lot of research, both fundamental and applied, has been carried out to investigate how catalysts work and to increase their efficiency. The present work shows how the use of Dark Field Microscopy (DFM) coupled with surface plasmon spectroscopy, enables the direct observation of the kinetics of H2 gas interaction with single gold nanorods (NR) coupled with Pt nanoparticles (NPs) and/or with metal oxide matrices. The plasmonic particles, gold NRs, act as optical probes, and enable the monitoring of the electron exchange through the measurement of their surface plasmon resonance (SPR) band shift. To improve the redox reaction kinetics, the Au NRs have been coupled with Pt NPs and embedded also into a TiO2 or ZnO low scattering matrix. The Au NRs, the Pt, TiO2 and ZnO NPs have been synthetized by colloid chemistry. Several samples made of bare Au NRs, or Au NRs coupled with only Pt NPs or with Pt and TiO2 NPs or with Pt and TiO2 have been deposited by spin coating on silica substrates. The longitudinal Au SPR band shift has been monitored by DFM looking at the variation of the scattering spectrum of a single Au NRs in the presence of H2. Time-resolved measurements have been also conducted at fixed wavelength in order to monitor the kinetics of the H2 reaction. With such measurements it was possible to elucidate the importance of the adsorbed oxygen and the TiO2 matrix on the H2 reaction with the Pt NPs.

Silver halide photochromic glasses doped with one of the transition metal oxides, (Ti O2) , (CoO) ,(Cr2 O3) are prepared using the melt quench technique. Glass samples are exposed to a UV source for 20 min. Spectral reflectance and transmittance at normal incidence of the prepared glasses are recorded before and after UV exposure with a double beam spectrophotometer in the spectral range 200-2500 nm. Dispersion parameters such as: single oscillator energy, dispersion energy and Abbe's number are deduced and compared. Absorption dispersion parameters, like optical energy gap for direct and indirect transitions, Urbach energy and steepness parameter, are deduced for the different glass prepared. Reflection loss, molar refractivity and electronic polarizability are deduced and compared. The effect of UV light exposure of these glasses on transmittance, reflectance, the linear and the predicted nonlinear optical parameters are investigated and discussed for the three transition metals. Nonlinear parameters increase in the three glass samples after UV exposure.

We report on the structural, electrical, and optical properties of 5% niobium doped TiO2 thin films grown on various substrates by pulsed laser deposition. The epitaxial anatase Nb:TiO2 film on LaAlO3 is shown to be an intrinsic transparent metal and its metallic property arises from Nb substitution into Ti site as evidenced by the Rutherford backscattering channeling result. In contrast, the rutile Nb:TiO2 thin films show insulating behaviors with 2-3 orders higher room temperature electrical resistivity and ˜30 times lower mobility. A blueshift in the optical absorption edge is observed in both phases, though of differing magnitude.

Silicene is an intriguing 2D topological material which is closely analogous to graphene but with stronger spin orbit coupling effect and natural compatibility with current silicon-based electronics industry. Here we demonstrate that silicene decorated with certain 3d transition metals (Vanadium) can sustain a stable quantum anomalous Hall effect using both analytical model and first-principles Wannier interpolation. We also predict the quantum valley Hall effect and electrically tunable topological states could be realized in certain transition metaldoped silicene where the energy band inversion occurs. Our findings provide new scheme for the realization of quantum anomalous Hall effect and platform for electrically controllable topological states which are highly desirable for future nanoelectronics and spintronics application.

The large-scale deployment of many types of fuel cells and electrolyzers is currently constrained by the lack of sustainable and efficient catalysts that can replace the less earth-abundant, noble metal-based catalysts, which are commonly used in these renewable energy systems. This burgeoning issue has led to explosive research efforts worldwide to find alternative, metal-free and noble metal-free catalysts that are composed of inexpensive and earth-abundant elements. Hence, the recent discoveries that doping carbon nanomaterials with heteroatoms (such as N, S, B, etc.) can give sustainable materials with good electrocatalytic activity for reactions carried out in fuel cells and electrolyzers have been not only quite exciting but also very promising to address these challenging issues. Interestingly, even though they contain no metals or involve only the inexpensive, more earth-abundant ones, the catalytic activity of some of these materials fares well with those of the commercially used noble metal-based electrocatalysts, such as Pt/C. However, research efforts to improve the catalytic activity, selectivity, and stability of some of these materials for various reactions are still necessary and thus continuing. While some of these efforts have focused on finding synthetic methods that can tune the structures and compositions of already known materials and thereby improve their catalytic properties (activity, selectivity, stability, etc.), others have focused on developing entirely new materials that can exhibit better or superior catalytic properties. In these efforts, additional considerations are also being paid to find facile synthetic routes or renewable and inexpensive precursors that can lead to such types of catalysts in order to make the entire process highly sustainable and widely applicable. In this Account, notable heteroatom-doped carbon catalysts that have been developed for reactions in fuel cells and water electrolyzers, the various synthetic

The electrochemical corrosion potential of 304 stainless steel coated under water by hyper-velocity oxy-fuel and plasma spray techniques using noble metaldoped powders was measured to evaluate the catalytic behavior in high temperature water under various water chemistry conditions. Thermal spray coatings of noble metaldoped powders exhibited catalytic behavior for the recombination of oxygen and hydrogen in high temperature water which causes the corrosion potential to decrease well below a critical value of {minus}230 mV{sub she} for the intergranular stress corrosion cracking protection in water. This was observed in water containing various amounts of oxygen and hydrogen peroxide when stoichiometric excess hydrogen was present.

A lean NOx catalyst and method of preparing the same is disclosed. The lean NOx catalyst includes a ceramic substrate, an oxide support material, preferably .gamma.-alumina, deposited on the substrate and a metal promoter or dopant introduced into the oxide support material. The metal promoters or dopants are selected from the group consisting of indium, gallium, tin, silver, germanium, gold, nickel, cobalt, copper, iron, manganese, molybdenum, chromium, cerium, vanadium, oxides thereof, and combinations thereof. The .gamma.-alumina preferably has a pore volume of from about 0.5 to about 2.0 cc/g; a surface area of between about 80 to 350 m.sup.2 /g; an average pore size diameter of between about 3 to 30 nm; and an impurity level of less than or equal to 0.2 weight percent. In a preferred embodiment the .gamma.-alumina is prepared by a sol-gel method, with the metaldoping of the .gamma.-alumina preferably accomplished using an incipient wetness impregnation technique.

We report the fabrication of degenerately doped silicon (Si) nanowires of different aspect ratios using a simple, low-cost and effective technique that involves metal-assisted chemical etching (MacEtch) combined with soft lithography or thermal dewetting metal patterning. We demonstrate sub-micron diameter Si nanowire arrays with aspect ratios as high as 180:1, and present the challenges in producing solid nanowires using MacEtch as the doping level increases in both p- and n-type Si. We report a systematic reduction in the porosity of these nanowires by adjusting the etching solution composition and temperature. We found that the porosity decreases from top to bottom along the axial direction and increases with etching time. With a MacEtch solution that has a high [HF]:[H(2)O(2)] ratio and low temperature, it is possible to form completely solid nanowires with aspect ratios of less than approximately 10:1. However, further etching to produce longer wires renders the top portion of the nanowires porous.

We report the fabrication of degenerately doped silicon (Si) nanowires of different aspect ratios using a simple, low-cost and effective technique that involves metal-assisted chemical etching (MacEtch) combined with soft lithography or thermal dewetting metal patterning. We demonstrate sub-micron diameter Si nanowire arrays with aspect ratios as high as 180:1, and present the challenges in producing solid nanowires using MacEtch as the doping level increases in both p- and n-type Si. We report a systematic reduction in the porosity of these nanowires by adjusting the etching solution composition and temperature. We found that the porosity decreases from top to bottom along the axial direction and increases with etching time. With a MacEtch solution that has a high [HF]:[H2O2] ratio and low temperature, it is possible to form completely solid nanowires with aspect ratios of less than approximately 10:1. However, further etching to produce longer wires renders the top portion of the nanowires porous.

Superconducting layered transition metal dichalcogenides (TMDs) stand out among other superconductors due to the tunable nature of the superconducting transition, coexistence with other collective electronic excitations (charge density waves), and strong intrinsic spin-orbit coupling. Molybdenum disulfide (MoS2) is the most studied representative of this family of materials, especially since the recent demonstration of the possibility to tune its critical temperature, Tc, by electric-field doping. However, just one of its polymorphs, band-insulator 2H-MoS2, has so far been explored for its potential to host superconductivity. We have investigated the possibility to induce superconductivity in metallic polytypes, 1T- and 1T'-MoS2, by potassium (K) intercalation. We demonstrate that at doping levels significantly higher than that required to induce superconductivity in 2H-MoS2, both 1T and 1T' phases become superconducting with Tc = 2.8 and 4.6 K, respectively. Unusually, K intercalation in this case is responsible both for the structural and superconducting phase transitions. By adding new members to the family of superconducting TMDs, our findings open the way to further manipulate and enhance the electronic properties of these technologically important materials.

Temperature is important because it has an effect on even the tiniest elements of daily life and is involved in a broad spectrum of human activities. That is why it is the most commonly measured physical quantity. Traditional temperature measurements encounter difficulties when used in some emerging technologies and environments, such as nanotechnology and biomedicine. The problem may be alleviated using optical techniques, one of which is luminescence thermometry. This paper reviews the state of luminescence thermometry and presents different temperature read-out schemes with an emphasis on those utilizing the downshifting emission of lanthanide-dopedmetal oxides and salts. The read-out schemes for temperature include those based on measurements of spectral characteristics of luminescence (band positions and shapes, emission intensity and ratio of emission intensities), and those based on measurements of the temporal behavior of luminescence (lifetimes and rise times). This review (with 140 references) gives the basics of the fundamental principles and theory that underlie the methods presented, and describes the methodology for the estimation of their performance. The major part of the text is devoted to those lanthanide-dopedmetal oxides and salts that are used as temperature probes, and to the comparison of their performance and characteristics.

Using density functional theory, we have theoretically studied dioxin binding on a graphene sheet or carbon nanotubes (CNT), finding that they can be effective adsorbents for dioxin in the presence of calcium atoms. This is due to a cooperative formation of sandwich complexes of graphene sheet or (5,5) CNT through the interaction pi-Ca-pi with the total binding energy of more than 3 eV. This correlates with the band structure analysis, which indicates charge transfer from the carbon systems and calcium atoms to dioxin when the molecule binds to the metal-doped carbon systems. For CNT with small radii, the relative strength of CNT-dioxin interaction is dependent on their chiralities. Upon dioxin binding, a large increase in the electronic density of states near the Fermi level also suggests that they can be used for dioxin sensing. Fe-doped CNT is also found to bind dioxin strongly, revealing an important role played by remnants of metallic catalysts in the chemical properties of CNT.

Cement clinker is the main component of Portland cement. It is composed of four main phases. One of them is the brownmillerite or the ferrite phase of cement clinker. It is prepared according to the formula (4CaO)(Al2O3)(Fe2O3)1-x (M) x , where M represents transition metal oxides (TMO): TiO2, Cr2O3, Mn2O3 and WO3, where x=1, 2, 3, 4 and 5 mol%. Each mixture was fired at 1300°C for 30 minutes in a platinum crucible. The samples were pulverized for Mössbauer spectroscopy, X-ray diffraction and a.c. conductivity measurements. A shift in the position of the characterized peaks of pure brownmillerite appears in the X-ray diffraction patterns of brownmillerite doped with a transition metal oxide. The a.c. conductivity showed a maximum value for the samples containing 3 mol% TiO2, Cr2O3 and Mn2O3, and 2 mol% WO3. The Mössbauer parameters for the sample containing 5 mol% M showed a gradual increase in the isomer shift values. The number of electrons in d-orbital for the doped transition atoms, as the nearest neighbor atoms increased from 2 to 5 electrons. The hyperfine magnetic field at Fe3+ (Oh) iron nucleus decreases with increasing M content. This may be due to the decrease of the particle size of brownmillerite.

ZnS quantum dots doped with magnetic transition metal (Zn1- x TM x S; where x = 0.04, 0.08 and transition metal = Ni, Mn, Fe, Co and Cr) were synthesized using a chemical co-precipitation method. To prevent agglomeration, samples were capped with polyvinylpyrrolidone. X-ray diffraction peaks confirmed pure cubic phases of all samples. The crystallite dimensions of the samples are within the scale of 2.0-2.6 nm, which was calculated using Scherrer formula. A band gap varying from 4.1 eV to 4.24 eV was estimated from their ultraviolet-visible absorption spectroscopy. The synthesized samples show a strong blue shift in their emission spectroscopy along with emissions from inherent Zn and S point defects (interstitial and vacancy). Superconducting quantum interference device studies at 300 K reveal that all samples show room temperature canted ferromagnetism at low magnetic fields which does not saturate even up to a fields of 5 T. We study the defects as seen through emission spectroscopy and correlate with the magnetic properties of the doped semiconducting quantum dots.

Transparent mesoporous silica plates doped with rare-earth metal oxide were prepared using solvent-evaporation method based on the self-organization between structure-directing agent and silicate in a non-aqueous solvent. A triblock copolymer, Pluronic (F127 or P123), was used as the structure-directing agent, while tetraethyl orthosilicate (TEOS) was used as a silica source. The pore diameter and the surface area of the mesoporous silica plate prepared with the optimized conditions were ca 40 A and 600 m2 g(-1), respectively, for both structure-directing agent. Rare-earth metal oxides (Eu, Tb, Tm oxide) in mesochannel were formed via one-step synthetic route based on the preparation method of a silica plate. Optical properties of rare-earth metal oxide-doped mesoporous silica plates were investigated by UV irradiation and photoluminescence (PL) spectroscopy. Under the exitation wavelength of 254 nm, the doped mesoporous silica plates emitted red, green and blue for Eu, Tb and Tm oxides, respectively. Rare-earth metal oxide-doped mesoporous silica plates showed enhanced PL intensity compared to that of the bulk rare-earth metal oxide.

Electronic state of charge carriers, in particular, in highly doped regions, in thin-film transistors of a semicrystalline conducting polymer poly(2,5-bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene), has been studied by using field-induced electron spin resonance (ESR) spectroscopy. By adopting an ionic-liquid gate insulator, a gate-controlled reversible electrochemical hole-doping of the polymer backbone is achieved, as confirmed from the change of the optical absorption spectra. The edge-on molecular orientation in the pristine film is maintained even after the electrochemical doping, which is clarified from the angular dependence of the g value. As the doping level increases, spin 1/2 polarons transform into spinless bipolarons, which is demonstrated from the spin-charge relation showing a spin concentration peak around 1%, contrasting to the monotonic increase in the charge concentration. At high doping levels, a drastic change in the linewidth anisotropy due to the generation of conduction electrons is observed, indicating the onset of metallic state, which is also supported by the temperature dependence of the spin susceptibility and the ESR linewidth. Our results suggest that semicrystalline conducting polymers become metallic with retaining their molecular orientational order, when appropriate doping methods are chosen.

Cuprous oxide (Cu{sub 2}O) flower-like nanostructures doped with various metal ions i.e. Fe, Co, Ni and Mn have been synthesized by an organic phase solution method. The powder X-ray diffraction study clearly reveals them as single phase simple cubic cuprite lattice. Study of their magnetic properties have shown that these doped samples are ferromagnetic in nature; however, no such property was observed for the undoped Cu{sub 2}O sample. The magnitude of the ferromagnetic behavior was found to be dependent on the dopant metal ions amount, which increased consistently with its increase. As total magnetic moment contribution of the dopedmetal ions calculated was insignificant, it is believed to have originated from the induced magnetic moments at cation deficiency sites in the material, created possibly due to the disturbance of the crystal lattice by the dopant ions. The existence of the defects has been supported by photoluminescence spectra of the doped samples. -- Graphical abstract: Room temperature ferromagnetic behavior was observed in the Cu{sub 2}O nanoflowers doped with Fe, Co, Ni and Mn ions. Cation deficiencies formed due to dopant ions were possibly responsible for ferromagnetism. Display Omitted

The disposal and reuse of waste printed circuit boards have been the major global concerns. Printed circuit boards, a form of Electronic waste (hereafter e-waste), have been chemically processed, doped with Ag(+), Cu(2+) and Sn(2+), and used as visible light photocatalysts against the degradation of methylene blue and methyl violet. The elemental analyses of pristine and metaldoped printed circuit board were obtained using energy dispersive X-ray fluorescence (EDXRF) spectra and inductively coupled plasma optical emission spectroscopy (ICP-OES). The morphology of parent and doped printed circuit board was obtained from scanning electron microscopy (SEM) measurements. The photocatalytic activity of parent and metaldoped samples was carried out for the decomposition of organic pollutants, methylene blue and methyl violet, under visible light irradiation. Metaldoped waste printed circuit boards (WPCBs) have shown higher photocatalytic activity against the degradation of methyl violet and methylene blue under visible light irradiation. Scavenger experiments were performed to identify the reactive intermediates responsible for the degradation of methylene blue and methyl violet. The reactive species responsible for the degradation of MV and MB were found to be holes and hydroxyl radicals. A possible mechanism of degradation of methylene blue and methyl violet is given. The stability and reusability of the catalysts are also investigated.

Gold nanorods, as an emerging noble metal nanomaterial with unique properties, have become the new exciting focus of theoretical and experimental studies in the past few years. The structure and function of gold nanorods, especially their biocompatibility, optical property, and photothermal effects, have been attracting more and more attention. Gold nanorods exhibit great potential in applications such as tumor molecular imaging and photothermal therapy. In this article, we review some of the main advances made over the past few years in the application of gold nanorods in surface functionalization, molecular imaging, and photothermal therapy. We also explore other prospective applications and discuss the corresponding concepts, issues, approaches, and challenges, with the aim of stimulating broader interest in gold nanorod-based nanotechnology and improving its practical application. PMID:23691482

Because of unusual properties and fascinating prospects for next-generation device applications, two-dimensional (2D) materials have attracted enormous attention since graphene was discovered in 2004. Among the 2D materials beyond graphene, group-IIIA metal-monochalcogenide (MX) monolayers (MLs), are receiving increasing interests because their excellent applications on electronics and optoelectronics. Recently, ferromagnetism and half-metallicity have been predicted in hole-doped GaS and GaSe MLs, which promise exciting potentials for semiconductor spintronics. Detection and measurement of spontaneous magnetization in these 2D materials will be essential for their spintronic applications. The magneto-optical (MO) effects not only are a powerful probe of magnetism in 2D materials but also have valuable applications in high-density data-storage technology. Furthermore, anomalous Hall effect is not only an ideal transport probe of itinerant magnetism but also of considerable current interest because of its topological nature. Here we perform a systematic first-principles density functional study on the MO Kerr and Faraday effects as well as such important magnetic and transport properties as magneto-crystalline anisotropy energy (MAE) and anomalous Hall conductivity (AHC) of all hole-doped MX (M = Ga, In; X = S, Se, Te) MLs. In this paper, we report the following important findings: (a) gate-tunable MO effects in MX MLs in a broad range of hole concentration; (b) large Kerr and Faraday rotation angles with Kerr angles comparable to well-known MO 3d-transition-metal multilayers and Faraday angles being among the largest ones reported; (c) tunable MAE and large AHC, making MX MLs suitable for magnetic memory devices current-driven via spin-transfer torque and also promising materials for magnetic field nanosensors with high sensitivity. Superior MO characteristics, together with the other interesting properties, would make MX MLs an excellent family of 2D materials for

YBa2Cu3O7 - x (YBCO) films with co-doping BaTiO3 (BTO) and Y2O3 nanostructures were prepared by metal organic deposition using trifluoroacetates (TFA-MOD). The properties of the BTO/Y2O3 co-doped YBCO films with different excess yttrium have been systematically studied by x-ray diffraction (XRD), Raman spectra, and scanning electron microscope (SEM). The optimized content of yttrium excess in the BTO/Y2O3 co-doped YBCO films is 10 mol.%, and the critical current density is as high as ˜17 mA/cm2 (self-field, 65 K) by the magnetic signal. In addition, the Y2Cu2O5 was formed when the content of yttrium excess increases to 24 mol.%, which may result in the deterioration of the superconducting properties and the microstructure. The unique combination of the different types of nanostructures of BTO and Y2O3 in the doped YBCO films, compared with the pure YBCO films and BTO doped YBCO films, enhances the critical current density (JC) not only at the self-magnetic field, but also in the applied magnetic field. Project supported by the National Natural Science Foundation of China (Grant No. 51272250), the National Basic Research Program of China (Grant No. 2011CBA00105), the National High Technology Research and Development Program of China (Grant No. 2014AA032702), and the Natural Science Foundation of Beijing, China (Grant No. 2152035).

A sandwich-structured photocatalyst shows an excellent performance in degradation reactions of a number of organic compounds under UV, visible light, and direct sunlight (see picture). The catalyst was synthesized by a combination of nonmetal doping and plasmonic metal decoration of TiO2 nanocrystals, which improves visible-light activity and enhances light harvesting and charge separation, respectively.

A porphyrin coordination polymer nanostructure comprising a network of pyridyl porphyrin molecules and coordinating metal ions coordinatively bound through the pyridyl groups. In some embodiments, the porphyrins are metalloporphyrins. A variety of nanostructures are formed by the network polymer, including nanospheres, polygonal nanostructures, nanorods, and nanofibers, depending on a variety of factors including coordination metal ion, porphyrin type, metal of the metalloporphyrin, and degree of agitation during nanostructure formation. Reduction of coordinating metal ions may be used to form metal nanoparticles on the coordination polymer nanostructure.

A porphyrin coordination polymer nanostructure comprising a network of pyridyl porphyrin molecules and coordinating metal ions coordinatively bound through the pyridyl groups. In some embodiments, the porphyrins are metalloporphyrins. A variety of nanostructures are formed by the network polymer, including nanospheres, polygonal nanostructures, nanorods, and nanofibers, depending on a variety of factors including coordination metal ion, porphyrin type, metal of the metalloporphyrin, and degree of agitation during nanostructure formation. Reduction of coordinating metal ions may be used to form metal nanoparticles on the coordination polymer nanostructure.

Electroplating sludges, once regarded as industrial wastes, are precious resources of various transition metals. This research has thus investigated the recycling of an electroplating sludge as a novel carbon-dopedmetal (Fe, Ni, Mg, Cu, and Zn) catalyst, which was different from a traditional carbon-supported metal catalyst, for effective NO selective catalytic reduction (SCR). This catalyst removed >99.7% NO at a temperature as low as 300 °C. It also removed NO steadily (>99%) with a maximum specific accumulative reduced amount (MSARA) of 3.4 mmol/g. Gas species analyses showed that NO removal was accompanied by evolving N2 and CO2. Moreover, in a wide temperature window, the sludge catalyst showed a higher CO2 selectivity (>99%) than an activated carbon-supported metal catalyst. Structure characterizations revealed that carbon-dopedmetal was transformed to metal oxide in the sludge catalyst after the catalytic test, with most carbon (2.33 wt %) being consumed. These observations suggest that NO removal over the sludge catalyst is a typical SCR where metals/metal oxides act as the catalytic center and carbon as the reducing reagent. Therefore, our report probably provides an opportunity for high value-added utilizations of heavy-metal wastes in mitigating atmospheric pollutions.

Similarly to polymer-supported assisted synthesis (PSAS), organic synthesis could be envisaged being performed by using zeolites, native or metal-doped, as heterogeneous catalysts. To illustrate this unprecedented Zeolite-Based Organic Synthesis (ZeoBOS), the total synthesis of acortatarin A was achieved through a novel strategy and using five out of eleven synthetic steps catalyzed by H- or metal-doped zeolites as catalysts. Notably, the formation of an yne-pyrrole intermediate with a copper-doped zeolite and the spiroketalization of an alkyne diol with a silver-doped zeolite have been developed as key steps of the synthesis.

We report the fabrication of near-vertically elongated GaN nanorods on quartz substrates. To control the preferred orientation and length of individual GaN nanorods, we combined molecular beam epitaxy (MBE) with pulsed-mode metal-organic chemical vapor deposition (MOCVD). The MBE-grown buffer layer was composed of GaN nanograins exhibiting an ordered surface and preferred orientation along the surface normal direction. Position-controlled growth of the GaN nanorods was achieved by selective-area growth using MOCVD. Simultaneously, the GaN nanorods were elongated by the pulsed-mode growth. The microstructural and optical properties of both GaN nanorods and InGaN/GaN core-shell nanorods were then investigated. The nanorods were highly crystalline and the core-shell structures exhibited optical emission properties, indicating the feasibility of fabricating III-nitride nano-optoelectronic devices on amorphous substrates.

A comparative study of different plasmonic nanoparticles with different morphologies (nanospheres and triangular nanoprisms) and metals (Ag and Au) was done in this work and applied to the ultrasensitive detection of aminoglutethimide (AGI) drug by surface enhanced Raman spectroscopy (SERS) and plasmon resonance. AGI is an aromatase inhibitor used as an antitumoral drug with remarkable pharmacological interest and also in illegal sport doping. The application of very sensitive spectroscopic techniques based on the localization of an electromagnetic field on plasmonic nanoparticles confirms the previous study of the adsorption of drugs onto a metal surface due to the near field character of these techniques. The adsorption of AGI on the above substrates was investigated at different pH values and surface coverages, and the results were analyzed on the basis of AGI/metal affinity, considering the interaction mechanism, the existence of two binding sites in AGI, and the influence of the interface on the adsorption in terms of surface charge due to the presence of other ions linked to the surface. Finally, a comparative quantitative detection of AGI was performed on both spherical and triangular nanoprism nanoparticles, and a limit of detection lower than those reported so far was deduced on the latter nanoparticles.

The ability to produce high-quality single-phase diluted magnetic semiconductors (DMS) is the driving factor to study DMS for spintronics applications. Fe-doped ZnO was synthesized by using a low-temperature co-precipitation technique producing Zn 1- x Fe x O nanoparticles ( x= 0, 0.02, 0.04, 0.06, 0.08, and 0.1). Structural, Raman, density functional calculations, and magnetic studies have been carried out in studying the electronic structure and magnetic properties of Fe-doped ZnO. The results show that Fe atoms are substituted by Zn ions successfully. Due to the small ionic radius of Fe ions compared to that of a Zn ions, the crystal size decreases with an increasing dopant concentration. First-principle calculations indicate that the charge state of iron is Fe 2+ and Fe 3+ with a zinc vacancy or an interstitial oxygen anion, respectively. The calculations predict that the exchange interaction between transition metal ions can switch from the antiferromagnetic coupling into its quasi-degenerate ferromagnetic coupling by external perturbations. This is further supported and explains the observed ferromagnetic bahaviour at magnetic measurements. Magnetic measurements reveal that decreasing particle size increases the ferromagnetism volume fraction. Furthermore, introducing Fe into ZnO induces a strong magnetic moment without any distortion in the geometrical symmetry; it also reveals the ferromagnetic coupling.

We demonstrate humidity sensors based on optical resonances sustained in sub-wavelength thick dye-doped polymer coatings on reflecting surfaces. As a result of coupling between dye molecular absorption and Fabry-Perot resonances in the air-coating-surface cavity, the absorption spectra of such thin-film structures show a strong resonant peak under certain illumination conditions. These resonances are sensitive to the structural and material properties of the thin-film, metal underlayer and ambient conditions and hence can be used for gas and vapor sensing applications. Specifically, we present our proof of principle experimental results for humidity sensing using a thin-film structure comprising Rhodamine6G-doped polyvinyl alcohol (PVA) films on silver substrates. Depending on the PVA film thickness, dye-concertation and angle of incidence, the resonant absorption peak can undergo either red-shift or blue-shift as RH level increases in the range 20% to 60%. Also, the absorption magnitude at certain wavelengths near to resonance show almost linear reduction which can be used as the sensing signal. Our simulation studies show a very good agreement with the experimental data. The spectral and temporal sensitivity of this thin-film structure is attributed to the changes in the thickness of the PVA layer which swells by absorbing water molecules

The ability to write 3D waveguides by femtosecond laser micromachining and the nonlinear refractive index (n2) spectrum of a new borate glass matrix, containing zinc and lead oxides - (BZP) have been investigated. The transparent matrix was doped with transition metals (CdCl2, Fe2O3, MnO2 and CoO) in order to introduce electronic transitions in visible spectrum, aiming to evaluate their influence on the waveguides and n2 spectrum. We observed that n2 is approximately constant from 600 to 1500 nm, exhibiting an average value of 4.5 × 10-20 m2/W, which is about twice larger than the one for fused silica. The waveguide profile is influenced by the self-focusing effect of the matrix owing to its positive nonlinear index of refraction in the wavelength used for micromachining. A decrease in the waveguide loss of approximately four times was observed for the sample doped with Fe in comparison to the other ones, which may be associated with the change in the optical gap energy.

Chromium dioxide (CrO{sub 2}) is a half metal that is of interest for spintronic devices. It has not been synthesized through traditional physical vapor deposition (PVD) techniques because of its thermodynamic instability in low oxygen pressures. Epitaxial thin films of Ru doped tetragonal rutile CrO{sub 2} were synthesized by a PVD technique. The as-deposited Ru{sub x}Cr{sub 1−x}O{sub 2} was ferrimagnetic with the saturation magnetization moment showing a strong dependence on the Ru concentration. Curie temperature as high as 241 K has been obtained for ∼23 at. % Ru. The Ru substitution increased the electrical conductivity by increasing the minority spin concentration. The spin polarization was found to be as high as 70% for 9 at. % Ru and decreased to ∼60% with Ru concentrations up to ∼44 at. %, which is determined by the Fermi velocities of the majority and minority spins. First principle calculations were performed to understand the effect of Ru content on the properties of CrO{sub 2}. The PVD processes of Ru doped CrO{sub 2} could lead to the practical applications of the high spin polarization of CrO{sub 2} in spintronic devices.

Our group works on improving the conversion efficiencies of terahertz (THz) wave generation using GaSe crystals. The operating principle is based on difference frequency generation (DFG) which has the advantages such as high output power, a single tunable frequency, and room temperature operation. In this study, GaSe crystals were grown by the temperature difference method under controlled vapor pressure (TDM-CVP). It is a liquid phase growth method with temperature 300 °C lower than that of the Bridgman method. Using this method, the point defects concentration is decreased and the polytype can be controlled. The transition metal Ti was used to dope the GaSe in order to suppress free carrier absorption in the low frequency THz region. As a result, a deep acceptor level of 38 meV was confirmed as being formed in GaSe with 1.4 at% Ti doping. Compared with undoped GaSe, a decrease in carrier concentration ( 1014 cm-3) at room temperature was also confirmed. THz wave transmittance measurements reveal the tendency for the absorption coefficient to increase as the amount of dopant is increased. It is expected that there is an optimum amount of dopant.

The ability to produce high-quality single-phase diluted magnetic semiconductors (DMS) is the driving factor to study DMS for spintronics applications. Fe-doped ZnO was synthesized by using a low-temperature co-precipitation technique producing Zn 1-x Fe x O nanoparticles (x= 0, 0.02, 0.04, 0.06, 0.08, and 0.1). Structural, Raman, density functional calculations, and magnetic studies have been carried out in studying the electronic structure and magnetic properties of Fe-doped ZnO. The results show that Fe atoms are substituted by Zn ions successfully. Due to the small ionic radius of Fe ions compared to that of a Zn ions, the crystal size decreases with an increasing dopant concentration. First-principle calculations indicate that the charge state of iron is Fe (2+) and Fe (3+) with a zinc vacancy or an interstitial oxygen anion, respectively. The calculations predict that the exchange interaction between transition metal ions can switch from the antiferromagnetic coupling into its quasi-degenerate ferromagnetic coupling by external perturbations. This is further supported and explains the observed ferromagnetic bahaviour at magnetic measurements. Magnetic measurements reveal that decreasing particle size increases the ferromagnetism volume fraction. Furthermore, introducing Fe into ZnO induces a strong magnetic moment without any distortion in the geometrical symmetry; it also reveals the ferromagnetic coupling.

Four different hybrid organic-inorganic materials based on TiO2-SiO2 matrices with organic additives and doped with rare-earth metal ions (III) from the group of europium, cerium, terbium, neodymium, dysprosium and samarium, were synthesized by sol-gel method. Tetraethyl orthosilicate, titanium (IV) isopropoxide and organic compounds, such as butyl acrylate, butyl methacrylate, ethyl acetoacetate, ethylene glycol dimethacrylate, ethyl acetate, propylene carbonate, organic solvents and certain inorganic salts were used in the synthesis. The inorganic part of the sols, which were used in the synthesis of all the hybrid materials, was prepared separately and then the organic parts were added. The materials obtained were aged for three weeks at room temperature and then heated in an electric oven for three hours at temperatures of 80 °C-150 °C. Scanning electron microscopy equipped with energy dispersive X-ray spectroscopy (SEM/EDX); X-ray diffraction (XRD); Fourier transform infrared spectroscopy (KBr technique); 29Si magic-angle spinning nuclear magnetic resonance; and fluorescence spectroscopy were used for the examination of morphology, microstructure and luminescence properties, respectively. Photoluminescence properties with relatively intense narrow emission lines of Tb, Eu, Dy, Nd, Sm respectively to the RE-ions doping, were observed for all the hybrid materials.

Rapid solid-state metathesis (SSM) reactions are often short-lived highly exothermic reactions that yield a molten alkali halide salt that aids in product growth and crystallization. SSM reactions may also produce kinetically stabilized structures due to the short (seconds) reaction times. This report describes the investigation of rapid SSM reactions in the synthesis of transition-metaldoped titanias (M-TiO2). The dopant targeted compositions were ten mol percent and based on elemental analysis, many of the M-TiO2 samples were close to this targeted level. Based on surface analysis, some samples showed large enrichment in surface dopant content, particularly chromium and manganese doped samples. Due to the highly exothermic nature of these reactions, rutile structured TiO2 was observed in all cases. The M-TiO2 samples are visible colored and show magnetic and optical properties consistent with the dopant in an oxide environment. UV and visible photocatalytic experiments with these visibly colored rutile M-TiO2 powders showed that many of them are strongly absorbent for methylene blue dye and degrade the dye under both UV and visible light illumination. This work may open up SSM reactions as an alternate non-thermodynamic reaction strategy for dopant incorporation into a wide range of oxide and non-oxides.

Thin films of Ti1-xAlxN were deposited on (100) Si by ultrahigh-vacuum dual-target reactive sputtering, and the impact of lightly doping Al of x as small as 0.09 on altering the films's microstructure upon thermal annealing, and hence the performance of the films (40nm thick) as diffusion barriers for Cu metallization was evaluated. The results of transmission electron microscopy, Rutherford backscattering spectroscopy, and grazing-incidence x-ray diffraction show that the TiN barrier layer gives the commonly observed voided, columnar grains composed of 5nm sized subgrains. Upon annealing, the subgrains tend to coalesce into 20nm sized equiaxed grains full of crystalline defects, initiating an inward penetration of Cu and a partial dissociation of TiN, transforming themselves, respectively, into pyramidal (or columnar) Cu3Si precipitates and a dendritic Ti5Si3 layer just after 550°C, 10min annealing. However, the lightly doped Al not only overrides the tendency to form intercolumnar voids inherent in sputter deposition by self-shadowing and statistical roughening, but also substantially enhances the microstructural and thermochemical stability, hence significantly improving barrier property, as evidenced from an annealing test at an elevated temperature (600°C) for a prolonged period of 30min.

Mesoporous aluminosilicate adsorbents for carbon dioxide were prepared by the grafting of aluminium into SBA-15 silica using an aqueous solution of aluminium chlorohydrate. As the ion exchange sites are primarily associated with the presence of tetrahedrally coordinated aluminium, extra-framework aluminium on the SBA-15 surface was inserted into the silica matrix by a treatment with an aqueous solution of NH(4)OH. Synthesized mesoporous aluminosilicate preserving all the characteristic features of a mesoporous molecular sieve was finally modified by the alkali metal cation exchange. To examine carbon dioxide adsorption on prepared materials, adsorption isotherms in the temperature range from 0 °C to 60 °C were measured. Based on the known temperature dependence of adsorption isotherms, isosteric adsorption heats giving information on the surface energetics of CO(2) adsorption were calculated and discussed. The comparison of carbon dioxide isotherms obtained on aluminosilicate SBA-15, aluminosilicate SBA-15 containing cations Na(+) and K(+) and activated alumina F-200 reveals that the doping with sodium or potassium cations dramatically enhances adsorption in the region of equilibrium pressures lower than 10 kPa. Therefore, synthesized aluminosilicate adsorbents doped with Na(+) or K(+) cations are suitable for carbon dioxide separation from dilute gas mixtures.

Rapid solid-state metathesis (SSM) reactions are often short-lived highly exothermic reactions that yield a molten alkali halide salt that aids in product growth and crystallization. SSM reactions may also produce kinetically stabilized structures due to the short (seconds) reaction times. This report describes the investigation of rapid SSM reactions in the synthesis of transition-metaldoped titanias (M–TiO{sub 2}). The dopant targeted compositions were ten mol percent and based on elemental analysis, many of the M–TiO{sub 2} samples were close to this targeted level. Based on surface analysis, some samples showed large enrichment in surface dopant content, particularly chromium and manganese doped samples. Due to the highly exothermic nature of these reactions, rutile structured TiO{sub 2} was observed in all cases. The M–TiO{sub 2} samples are visible colored and show magnetic and optical properties consistent with the dopant in an oxide environment. UV and visible photocatalytic experiments with these visibly colored rutile M–TiO{sub 2} powders showed that many of them are strongly absorbent for methylene blue dye and degrade the dye under both UV and visible light illumination. This work may open up SSM reactions as an alternate non-thermodynamic reaction strategy for dopant incorporation into a wide range of oxide and non-oxides.

In the present paper, we study the nonlinear optical response of the bimetal composites doped with metal nanoparticles in the framework of nonlinear Mie theory combined with the Maxwell-Garnett model. We concentrate on the second-order harmonic generation from bimetal nanocomposites including silver and gold particles, since sometimes the nonlinear optical response is sensitive to the more accurate of material structure than linear optical response. We show that optical second harmonic generation is strongly sensitive to temperature as an environmental parameter, interparticle plasmon coupling between Au and Ag nanoparticles (the filling factor of inclusions), the particle size and the surrounding medium. However, this work shows good potential of bimetal composites for nonlinear optics at the nanoscale.

New results obtained by applying positron annihilation spectroscopy to the investigation of zirconia-based nanomaterials doped with metal cations of different valence are reported. The slow-positron implantation spectroscopy combined with Doppler broadening measurements was employed to study the sintering of pressure-compacted nanopowders of tetragonal yttria-stabilised zirconia (t-YSZ) and t-YSZ with chromia additive. Positronium (Ps) formation in t-YSZ was proven by detecting 3γ-annihilations of ortho-Ps and was found to gradually decrease with increasing sintering temperature. A subsurface layer with enhanced 3γ-annihilations, compared to the deeper regions, could be identified. Addition of chromia was found to inhibit Ps formation. In addition, first results of positron lifetime measurements on nanopowders of zirconia phase-stabilised with MgO and CeO2 are presented.

We theoretically investigate the electronic spin relaxation effect in the hole-doped monolayer and bilayer transition-metal dichalcogenides in the presence of the crystal defects. We simulate lattice vacancies in the multi-orbital tight-binding model obtained by the first-principle method and actually estimate the spin relaxation rate by using the tight-binding model. In the monolayer, the spin-relaxation time is found to be much longer than the momentum relaxation time, and this is attributed to the fact that the spin hybridization in the band structure is suppressed by the mirror reflection symmetry. The bilayer TMD has a much shorter spin relaxation time in contrast because of the stronger spin hybridization due to the absence of the mirror symmetry.

Photoluminescence (PL), time-resolved PL, and photoreflectance spectroscopy are applied to InP doping superlattices grown by metal organic chemical vapor deposition. It is observed that the emission peak and line shape depend on the optical excitation intensity; the peak of the CW PL spectrum increases in energy with the intensity of the pumping light; the highest energy peak is at 888 nm; and the time-resolved PL exhibits long decay times. The energy separation of the quantized subbands is studied by measuring the PR spectra of two samples. The measurements reveal that PR line shapes are explained by photomodulation of the subbands in the conduction band; these line shapes account for the dependence of the spectrum on the power of the exciting light and on the layer thickness.

Density functional theory calculations were carried out to characterize a series of transition-metal-doped aluminum hydrides, forming TMAl(n)H(2n) and TMAl(n)H(2n+1) (TM = Sc, Ti, V; n = 3,4), in either charged or neutral form. A new electron-counting rule for these clusters was formulated as PSEN (paired skeleton electron number) = 4n, which can characterize both closed-shell and open-shell clusters. On the basis of this electron-counting rule, the superatomic clusters such as TiAl(4)H(9) and TiAl(3)H(6) were identified and can be used to assemble supramolecular structures. Electronic structure analysis showed that three-centered TM-H-Al bonds largely contributed to the structural stability. Also, the spin state of a wide range of clusters in their ground state can be predicted by the electron-counting rule.

We perform an investigation into the properties of Pr{sup 3+}:Y{sub 2}SiO{sub 5} whispering-gallery-mode resonators as a first step toward achieving the strong coupling regime of cavity QED with rare-earth-metal-ion-doped crystals. Direct measurement of cavity QED parameters are made using photon echoes, giving good agreement with theoretical predictions. By comparing the ions at the surface of the resonator to those in the center, it is determined that the physical process of making the resonator does not negatively affect the properties of the ions. Coupling between the ions and resonator is analyzed through the observation of optical bistability and normal-mode splitting.

Highlights: • ZnO nanorods were grown on Au and Ag films in aqueous solution by galvanic effect. • The method is prone to metal contamination which can influence the ZnO properties. • Iron doping improves the lattice matching between ZnO and the substrate. • Energy levels of point defects are lowered and the light emission is red-shifted. • Galvanic-induced nucleation starts and proceeds continuously during the growth. - Abstract: Dense arrays of vertically aligned ZnO nanorods have been grown onto either silver or gold seedless substrates trough a simple hydrothermal method by exploiting the galvanic effect between the substrate and metallic parts. The nanorods exhibit larger bases and more defined hexagonal shapes, in comparison with standard non-galvanic wet-chemistry synthesis. X-ray diffraction (XRD) shows that the iron contamination, associated with the galvanic contact, significantly improves the in-plane compatibility of ZnO with the Au and Ag cubic lattice. Photoluminescence (PL) measurements indicate that the contamination does not affect the number density of localized defects, but lowers their energy levels uniformly; differently, the band-edge emission is not altered appreciably. Finally, we have found that the ZnO hetero-nucleation by galvanic effect initiates at different times in different sites of the substrate area. Our results can be useful for the fabrication of high performance piezonanodevices comprising high-density metal-to-ZnO nanoscaled junctions without intermediate polycrystalline layers.

Although the properties of extraordinary optical transmission (EOT) due surface plasmon polariton (SPP), which are coupled in metallic slits have been widely studied in the last two decades, their influence on the absorption and transmission spectra from their dielectric substrates has not been deserved the same attention. The choice of a good substrate for implementation not just for gratings, but also for other devices, it is extremely important in order to achieve great applications of the EOT. Good candidates to replace the conventional semiconductor based substrates are the rare earth ions (REI) doped glasses. The specific case of Erbium ions and its implementation into glasses for the fabrication of fiber optics, as Erbium doped fiber amplifiers (EDFA). The transmission observed through the plasmonic nanostructures is elucidated considering the following effects: (i) white light absorption by the Er3+ ions, (ii) coupling between the light and the nanostructure via the creation of surface plasmon polariton where the wavelengths with minimums transmission corresponds to the 4I15/2 → [2H9/2, 4F3/2, 4F5/2, 4F7/2, 2H11/2, 4S3/2, 4F9/2] absorption levels the Er3+, which propagates through the slits, and, finally, (iii) the Er3+ transmission intensity and the spectral shape -symmetry depend on the nature of metallic film and the number of slits constituting the arrays, for which the resonant properties are strongly affected. Furthermore, in order to compare the influence of substrate in the transmission properties, we also performed the same measurements on slit arrays fabricated on the BK 7 glass.

We have investigated the structural and magnetic properties of Li doped graphitic carbon nitride (g-C{sub 4}N{sub 3}) using the van der Waals density functional theory. A free standing g-C{sub 4}N{sub 3} was known to show a half metallic state with buckling geometry, but this feature completely disappears in the presence of Li doping. Besides this structural modification, very interestingly, we have obtained that the Li doped g-C{sub 4}N{sub 3} shows dramatic change in its electronic structure. Both ferromagnetic and nonmagnetic states are almost degenerated in one Li atom doped system. However, the transition from half metallic state to semiconductor is observed with further increase of Li concentration and the calculated energy gap is 1.97 eV. We found that Li impurity plays as a donor element and charge transfer from the Li atom to neighboring N atoms induces a band gap. Overall, we have observed that the electronic and magnetic properties of g-C{sub 4}N{sub 3} are substantially modified by Li doping.

Organic solar cells are flexible and inexpensive, and expected to have a wide range of applications. Many transparent organic solar cells have been reported and their success hinges on full transparency and high power conversion efficiency. Recently, carbon nanotubes and graphene, which meet these criteria, have been used in transparent conductive electrodes. However, their use in top electrodes has been limited by mechanical difficulties in fabrication and doping. Here, expensive metal top electrodes were replaced with high-performance, easy-to-transfer, aerosol-synthesized carbon nanotubes to produce transparent organic solar cells. The carbon nanotubes were p-doped by two new methods: HNO3 doping via ‘sandwich transfer’, and MoOx thermal doping via ‘bridge transfer’. Although both of the doping methods improved the performance of the carbon nanotubes and the photovoltaic performance of devices, sandwich transfer, which gave a 4.1% power conversion efficiency, was slightly more effective than bridge transfer, which produced a power conversion efficiency of 3.4%. Applying a thinner carbon nanotube film with 90% transparency decreased the efficiency to 3.7%, which was still high. Overall, the transparent solar cells had an efficiency of around 50% that of non-transparent metal-based solar cells (7.8%). PMID:27527565

We report the effect of oxygen partial pressure (OPP) and 5% Fe doping on the structural, electrical, and magnetic properties of MoOx thin films on c-Al2O3 substrate prepared by pulsed laser deposition technique. Detailed analyses of the structural properties suggest that the grown phase of molybdenum oxides and its orientation strongly depend on the OPP as well as Fe doping. Undoped and Fe doped α-MoO3 films formed at 350 mTorr OPP value show insulating character, where as MoO2 films formed at lower OPP values reveal metallic behavior. Resistivity minima are observed in Fe doped MoO2 films, which could be due to weak localization effect or Kondo scattering of the conduction electrons from the Fe impurities. Interestingly, all the Fe doped molybdenum oxide films show magnetic hysteresis at room temperature irrespective of their insulating (MoO3 phase) or metallic (MoO2 phase) behavior.

Organic solar cells are flexible and inexpensive, and expected to have a wide range of applications. Many transparent organic solar cells have been reported and their success hinges on full transparency and high power conversion efficiency. Recently, carbon nanotubes and graphene, which meet these criteria, have been used in transparent conductive electrodes. However, their use in top electrodes has been limited by mechanical difficulties in fabrication and doping. Here, expensive metal top electrodes were replaced with high-performance, easy-to-transfer, aerosol-synthesized carbon nanotubes to produce transparent organic solar cells. The carbon nanotubes were p-doped by two new methods: HNO3 doping via ‘sandwich transfer’, and MoOx thermal doping via ‘bridge transfer’. Although both of the doping methods improved the performance of the carbon nanotubes and the photovoltaic performance of devices, sandwich transfer, which gave a 4.1% power conversion efficiency, was slightly more effective than bridge transfer, which produced a power conversion efficiency of 3.4%. Applying a thinner carbon nanotube film with 90% transparency decreased the efficiency to 3.7%, which was still high. Overall, the transparent solar cells had an efficiency of around 50% that of non-transparent metal-based solar cells (7.8%).

Organic solar cells are flexible and inexpensive, and expected to have a wide range of applications. Many transparent organic solar cells have been reported and their success hinges on full transparency and high power conversion efficiency. Recently, carbon nanotubes and graphene, which meet these criteria, have been used in transparent conductive electrodes. However, their use in top electrodes has been limited by mechanical difficulties in fabrication and doping. Here, expensive metal top electrodes were replaced with high-performance, easy-to-transfer, aerosol-synthesized carbon nanotubes to produce transparent organic solar cells. The carbon nanotubes were p-doped by two new methods: HNO3 doping via 'sandwich transfer', and MoOx thermal doping via 'bridge transfer'. Although both of the doping methods improved the performance of the carbon nanotubes and the photovoltaic performance of devices, sandwich transfer, which gave a 4.1% power conversion efficiency, was slightly more effective than bridge transfer, which produced a power conversion efficiency of 3.4%. Applying a thinner carbon nanotube film with 90% transparency decreased the efficiency to 3.7%, which was still high. Overall, the transparent solar cells had an efficiency of around 50% that of non-transparent metal-based solar cells (7.8%).

The present work describes the glass samples of composition (x% V₂O₅-(80-x)% B₂O₃-20% Na₂CO₃) VBS glass system and (x%MnO₂-(80-x)% B₂O₃-20% Na₂CO₃) in MBS glass system with mol% ranging from x=3, 6, 9, 12, 15 and 18 in steps of 3 mol% are prepared by melt quenching technique. For these prepared glass systems, sound velocity (longitudinal and shear velocities) and density have been measured. The sound velocity (longitudinal and shear) was measured by using pulse-echo technique at 5 MHz. The XRD study was carried to out to ascertain the amorphous nature of the glass specimen. Using these measured values, the elastic moduli, Poisson's ratio, Debye temperature, acoustic impedance and thermal expansion coefficient of the two glass systems were evaluated. The elastic and mechanical properties of the prepared glass systems are analyzed from ultrasonic study and the structural characterization from spectroscopic study. The effects due to the doping of transition metal ions with borate have been discussed. In the V₂O₅ doped glass system,(VBS glass system) the sound velocity, density and elastic moduli, steeply increases after 12 mol% comparatively with MnO₂ doped glass system (VBS glass system). The present study critically observes the doping of V₂O₅ with borate enhances the strengthening of network linkage and hardening of the glassy network structure than MnO₂. The IR spectral analysis reveals depolymerization of the borate network and conversion of BO₃ or BO4 units with the formation of non-bridging oxygen. The FTIR spectral studies confirm the presence of various functional groups of the sample. FTIR spectrum of sample exhibits broad absorption bands indicating the wide distribution of borate structural units. The effect of Na₂CO₃, V₂O₅ and MnO₂ contents on the structures of borate glass is evaluated from the FTIR spectra. The topological aspects of the prepared glass samples are exhaustively reported from SEM micrographs.

The present work describes the glass samples of composition (x% V2O5-(80-x)% B2O3-20% Na2CO3) VBS glass system and (x% MnO2-(80-x)% B2O3-20% Na2CO3) in MBS glass system with mol% ranging from x = 3, 6, 9, 12, 15 and 18 in steps of 3 mol% are prepared by melt quenching technique. For these prepared glass systems, sound velocity (longitudinal and shear velocities) and density have been measured. The sound velocity (longitudinal and shear) was measured by using pulse-echo technique at 5 MHz. The XRD study was carried to out to ascertain the amorphous nature of the glass specimen. Using these measured values, the elastic moduli, Poisson's ratio, Debye temperature, acoustic impedance and thermal expansion coefficient of the two glass systems were evaluated. The elastic and mechanical properties of the prepared glass systems are analyzed from ultrasonic study and the structural characterization from spectroscopic study. The effects due to the doping of transition metal ions with borate have been discussed. In the V2O5 doped glass system, (VBS glass system) the sound velocity, density and elastic moduli, steeply increases after 12 mol% comparatively with MnO2 doped glass system (VBS glass system). The present study critically observes the doping of V2O5 with borate enhances the strengthening of network linkage and hardening of the glassy network structure than MnO2. The IR spectral analysis reveals depolymerization of the borate network and conversion of BO3 or BO4 units with the formation of non-bridging oxygen. The FTIR spectral studies confirm the presence of various functional groups of the sample. FTIR spectrum of sample exhibits broad absorption bands indicating the wide distribution of borate structural units. The effect of Na2CO3, V2O5 and MnO2 contents on the structures of borate glass is evaluated from the FTIR spectra. The topological aspects of the prepared glass samples are exhaustively reported from SEM micrographs.

The lowest-energy structures of neutral and cationic Ge nM (n = 9, 10; M = Si, Li, Mg, Al, Fe, Mn, Pb, Au, Ag, Yb, Pm and Dy) clusters were studied by genetic algorithm (GA) and first-principles calculations. The calculation results show that doping of the metal atoms and Si into Ge9 and Ge10 clusters is energetically favorable. Most of the metal-doped Ge cluster structures can be viewed as adding or substituting metal atom on the surface of the corresponding ground-state Gen clusters. However, the neutral and cationic FeGe9,10,MnGe9,10 and Ge10Al are cage-like with the metal atom encapsulated inside. Such cage-like transition metaldoped Gen clusters are shown to have higher adsorption energy and thermal stability. Our calculation results suggest that Ge9,10Fe and Ge9Si would be used as building blocks in cluster-assembled nanomaterials because of their high stabilities.

The lowest-energy structures of neutral and cationic Ge{sub n}M (n = 9, 10; M = Si, Li, Mg, Al, Fe, Mn, Pb, Au, Ag, Yb, Pm and Dy) clusters were studied by genetic algorithm (GA) and first-principles calculations. The calculation results show that doping of the metal atoms and Si into Ge{sub 9} and Ge{sub 10} clusters is energetically favorable. Most of the metal-doped Ge cluster structures can be viewed as adding or substituting metal atom on the surface of the corresponding ground-state Ge{sub n} clusters. However, the neutral and cationic FeGe{sub 9,10},MnGe{sub 9,10} and Ge{sub 10}Al are cage-like with the metal atom encapsulated inside. Such cage-like transition metaldoped Ge{sub n} clusters are shown to have higher adsorption energy and thermal stability. Our calculation results suggest that Ge{sub 9,10}Fe and Ge{sub 9}Si would be used as building blocks in cluster-assembled nanomaterials because of their high stabilities.

A methodology providing access to dumbbell-tipped, metal-semiconductor and metal oxide-semiconductor heterostructured nanorods has been developed. The synthesis and characterization of CdSe@CdS nanorods incorporating ferromagnetic cobalt nanoinclusions at both nanorod termini (i.e., dumbbell morphology) are presented. The key step in the synthesis of these heterostructured nanorods was the decoration of CdSe@CdS nanorods with platinum nanoparticle tips, which promoted the deposition of metallic CoNPs onto Pt-tipped CdSe@CdS nanorods. Cobalt nanoparticle tips were then selectively oxidized to afford CdSe@CdS nanorods with cobalt oxide domains at both termini. In the case of longer cobalt-tipped nanorods, heterostructured nanorods were observed to self-organize into complex dipolar assemblies, which formed as a consequence of magnetic associations of terminal CoNP tips. Colloidal polymerization of these cobalt-tipped nanorods afforded fused nanorod assemblies from the oxidation of cobalt nanoparticle tips at the ends of nanorods via the nanoscale Kirkendall effect. Wurtzite CdS nanorods survived both the deposition of metallic CoNP tips and conversion into cobalt oxide phases, as confirmed by both XRD and HRTEM analysis. A series of CdSe@CdS nanorods of four different lengths ranging from 40 to 174 nm and comparable diameters (6-7 nm) were prepared and modified with both cobalt and cobalt oxide tips. The total synthesis of these heterostructured nanorods required five steps from commercially available reagents. Key synthetic considerations are discussed, with particular emphasis on reporting isolated yields of all intermediates and products from scale up of intermediate precursors.

Central in material design of metal oxides is the increase of surface area and control of intrinsic electronic and optical properties, because of potential applications for energy storage, photocatalysis and photovoltaics. Here, we disclose a facile method, inspired by geochemical process, which gives rise to mesoporous anion-dopedmetal oxides. As a model system, we demonstrate that simple calcination of a multinuclear coordination cluster results in synchronic chemical reactions: thermal oxidation of Ti8O10(4-aminobenzoate)12 and generation of gases including amino-group fragments. The gas generation during the thermal oxidation of Ti8O10(4-aminobenzoate)12 creates mesoporosity in TiO2. Concurrently, nitrogen atoms contained in the gases are doped into TiO2, thus leading to the formation of mesoporous N-doped TiO2. The mesoporous N-doped TiO2 can be easily synthesized by calcination of the multinuclear coordination cluster, but shows better photocatalytic activity than the one prepared by a conventional sol-gel method. Owing to an intrinsic designability of coordination compounds, this facile synthetic will be applicable to a wide range of metal oxides and anion dopants. PMID:26681104

Central in material design of metal oxides is the increase of surface area and control of intrinsic electronic and optical properties, because of potential applications for energy storage, photocatalysis and photovoltaics. Here, we disclose a facile method, inspired by geochemical process, which gives rise to mesoporous anion-dopedmetal oxides. As a model system, we demonstrate that simple calcination of a multinuclear coordination cluster results in synchronic chemical reactions: thermal oxidation of Ti8O10(4-aminobenzoate)12 and generation of gases including amino-group fragments. The gas generation during the thermal oxidation of Ti8O10(4-aminobenzoate)12 creates mesoporosity in TiO2. Concurrently, nitrogen atoms contained in the gases are doped into TiO2, thus leading to the formation of mesoporous N-doped TiO2. The mesoporous N-doped TiO2 can be easily synthesized by calcination of the multinuclear coordination cluster, but shows better photocatalytic activity than the one prepared by a conventional sol-gel method. Owing to an intrinsic designability of coordination compounds, this facile synthetic will be applicable to a wide range of metal oxides and anion dopants.

Praseodymium hydroxide nanorods were synthesized by a two-step approach: First, metallic praseodymium was used to form praseodymium chloride, which reacted subsequently with KOH solution to produce praseodymium hydroxide. In the second step the hydroxide was treated with a concentrated alkaline solution at 180 degrees C for 45 h, yielding nanorods as shown by the scanning and transmission electron microscopy images. The results of X-ray diffraction and energy-dispersive X-ray spectroscopy experiments indicate that these nanorods are pure praseodymium hydroxide with a hexagonal structure, which can be converted into praseodymium oxide (Pr6O11) nanorods of a face-centered cubic structure after calcination at 600 degrees C for 2 h in air. Gold was loaded on the praseodymium oxide nanorods using HAuCl4 as the gold source, and NaBH4 was used to reduce the gold species to metallic nanoparticles with sizes of 8-12 nm on the nanorod surface. These Au/Pr6O11 nanorods exhibit superior catalytic activity for CO oxidation.

A multicolored photoluminescent hybrid system based on lanthanide ions-dopedmetal organic frameworks/silica composite host has potential in display and barcode applications. By controlling the stoichiometry of the lanthanides via cation exchange, proportional various lanthanide ions are successfully introduced into metal organic frameworks, whose emission intensity is correspondingly proportional to its amount. The resulting luminescent barcodes depend on the lanthanide ions ratios and compositions. Subsequently, the lanthanide ions located in the channels of metal organic frameworks are protected from any interaction with the environment after the modification of silica on the surface. The optical and thermal stability of the hybrid materials are improved for technological application.

Density functional theory calculations were performed to elucidate the underlying physics describing the adsorption energies on doped late transition metal dioxide rutiles. Adsorption energies of atomic oxygen on doped rutiles M{sup D}-M{sup H}O{sub 2}, where transition metal M{sup D} is doped into M{sup H}O{sub 2}, were expressed in terms of a contribution from adsorption on the pure oxide of the dopant M{sup D} and perturbations to this adsorption energy caused by changing its neighboring metal cations and lattice parameters to that of the host oxide M{sup H}O{sub 2}, which we call the ligand and strain effects, respectively. Our analysis of atom projected density of states revealed that the t{sub 2g}-band center had the strongest correlation with adsorption energies. We show that charge transfer mediated shifts to the t{sub 2g}-band center describe the ligand effect, and the radii of the atomic orbitals of metal cations can predict the magnitude and direction of this charge transfer. Strain produces systematic shifts to all features of the atom projected density of states, but correlations between the strain effect and the electronic structure were dependent on the chemical identity of the metal cation. The slope of these correlations can be related to the idealized d-band filling. This work elucidates the underlying physics describing adsorption on doped late transition metal oxides and establishes a foundation for models that use known chemical properties for the prediction of reactivity.

Currently, there is enormous interest in research, development and optimization of the combustion processes for energy harvesting. Recent statistical and economic analyses estimated that by improving the coal-based firing/combustion processes in the power plants, savings up to $450-500 million yearly can be achieved. Advanced sensors and controls capable of withstanding extreme environments such as high temperatures, highly corrosive atmospheres, and high pressures are critical to such efficiency enhancement and cost savings. For instance, optimization of the combustion processes in power generation systems can be achieved by sensing, monitoring and control of oxygen, which is a measure of the completeness of the process and can lead to enhanced efficiency and reduced greenhouse gas emissions. However, despite the fact that there exists a very high demand for advanced sensors, the existing technologies suffer from poor 'response and recovery times' and 'long-term stability.' Motivated by the aforementioned technological challenges, the present work was focused on high-temperature (≥700 °C) oxygen sensors for application in power generation systems. The objective of the present work is to investigate nanostructured gallium oxide (2O3) based sensors for oxygen sensing, where we propose to conduct in-depth exploration of the role of refractory metal (tungsten, W, in this case) doping into 2O 3 to enhance the sensitivity, selectivity, stability ("3S" criteria) and reliability of such sensors while keeping cost economical. Tungsten (W) doped gallium oxide (2O3) thin films were deposited via rf-magnetron co-sputtering of W-metal and Ga2O3-ceramic targets. Films were produced by varying the sputtering power applied to the W-target in order to achieve variable W content into 2O3 films while substrate temperature was kept constant at 500 °C. Chemical composition, chemical valence states, microstructure and crystal structure of as-grown and post-annealed W-doped 2O3

The plasmon coupling between metal nanocrystals can lead to large plasmon shifts, enormous electric field enhancements, and new plasmon modes. Metalnanorods, unlike spherical ones, possess a transverse and a longitudinal plasmon mode owing to their geometrical anisotropy. Consequently, the plasmon coupling between metalnanorods is much more complicated than that between nanospheres. For the latter, experimental approaches, simple scaling relationships, and exact analytic solutions have been developed for describing the plasmon coupling. In this study, we have carried out extensive finite-difference time-domain simulations to understand the plasmon coupling in the dimers of Au nanorods that are aligned along their length axes. The effects of the gap distance, longitudinal plasmon energy, and end shape of the nanorod monomers on the plasmon coupling have been scrutinized. The coupling energy diagrams show a general anticrossing behavior. All of them can be rescaled into one simple and universal hyperbolic formula. A theoretical model based on two interacting mechanical oscillators has been developed to understand the plasmon coupling between two arbitrarily varying Au nanorods. This model, together with the universal equation, allows for the determination of the coupled plasmon energies of Au nanorod dimers with high accuracies. Furthermore, the Fano interference has been observed in the nanorod heterodimers, with its behavior being dependent on the gap distance and plasmon energies of the nanorod monomers. Our results will be useful for predicting the coupled plasmon energies of metalnanorod dimers in a variety of plasmonic applications and understanding the Fano resonance in plasmonic nanostructures.

There are instances that bimetal doped semiconductor materials impart superior photocatalytic activity than bare and mono-metaldoping. In this study, visible light responsive mono- (Cu/TiO2 and Ni/TiO2) and bi-metaldoped (Cu-Ni/TiO2) TiO2 photocatalysts with wide band gap energy were synthesized via co-precipitation method with an equal mass ratio of Cu and Ni. The catalyst characterization was performed using Diffuse Reflectance UV-visible (DR-UV-vis) spectroscopy, Fourier Transform Infrared (FTIR) spectroscopy, X-ray Diffraction (XRD), zeta-potential and Transmission Electron Microscopy (TEM) analyzes. The charge balancing effect of Cu and Ni caused a notable reduction in the optical band gap of TiO2 to 2.91 eV with Cu-Ni/TiO2. The synthesis method increased the anatase phase significantly along with the crystallite size. Cu-Ni/TiO2 displayed a lesser destabilization tendency, and the absolute value of zeta-potentials increased much at pH > pHzpc resulted from the higher oxygen vacancies. The activity of Ni/TiO2, Cu/TiO2, and Cu-Ni/TiO2 was tested for the degradation dynamics and kinetics of Eriochrome Cyanine Red (ECR), an anionic dye. Cu doping exhibited a better dye decomposition because of the low recombination rate of electron/hole pair as a full 3d sub-level of Cu is energetically more favorable than a full 4s sub-level of Ni. The mechanism of dye decomposition releasing inorganic ions is also proposed and validated from the mass spectra.

Using the first-principles density functional approach, we investigate Ca2FeOsO6, a material of double perovskite structure synthesized recently. According to the calculations, Ca2FeOsO6 is a ferrimagnetic Mott-insulator with the total magnetic moment {μ }{tot}= 4 {μ }{{B}} per unit cell. The system is found to be influenced by the cooperative effect of spin-orbit coupling (SOC) and Coulomb interactions of Fe-3d and Os-5d electrons, in addition to the crystal field. When Fe is replaced with Ni, the system exhibits half metallic (HM) states desirable for spintronic applications. In [Ca2Fe1-x Ni x OsO6]2, HM ferrimagnetism is observed with {μ }{tot}=2 {μ }{{B}} per unit cell for doping rate x = 0.5, whereas HM antiferromagnetism (HMAFM) with nearly zero spin magnetization in the unit cell is achieved for x = 1 respectively. It is emphasized that half metallicity is retained in presence of SOC due to the large exchange-splitting between spin-up and spin-down bands close to the Fermi level.

The pressure dependence of the superconducting transition temperature (Tc) and unit cell metrics of tetragonal (NH3)yCs0.4FeSe were investigated in high pressures up to 41 GPa. The Tc decreases with increasing pressure up to 13 GPa, which can be clearly correlated with the pressure dependence of c (or FeSe layer spacing). The Tc vs. c plot is compared with those of various (NH3)yMxFeSe (M: metal atoms) materials exhibiting different Tc and c, showing that the Tc is universally related to c. This behaviour means that a decrease in two-dimensionality lowers the Tc. No superconductivity was observed down to 4.3 K in (NH3)yCs0.4FeSe at 11 and 13 GPa. Surprisingly, superconductivity re-appeared rapidly above 13 GPa, with the Tc reaching 49 K at 21 GPa. The appearance of a new superconducting phase is not accompanied by a structural transition, as evidenced by pressure-dependent XRD. Furthermore, Tc slowly decreased with increasing pressure above 21 GPa, and at 41 GPa superconductivity disappeared entirely at temperatures above 4.9 K. The observation of a double-dome superconducting phase may provide a hint for pursuing the superconducting coupling-mechanism of ammoniated/non-ammoniated metal-doped FeSe.

The lack of high efficiency thermoelectric materials hinders their deployment into wide ranging applications such as power generation from waste heat and solid state heating and cooling, which could lead to significant energy savings. Type I clathrates have recently been identified as prospective thermoelectric materials for power generation purposes due to their very low lattice thermal conductivity values. The maximum thermoelectric figure of merit of almost all type I clathrates is, however, less than 1; and occurs at, or above, 1000 K making them unfavorable especially for intermediate temperature applications. In this report, we demonstrate that transition metaldoping introduces charge distortion and lattice defects into these materials which increases the ionized impurity scattering of carriers and point defect scattering of lattice phonons, respectively; leading to an enhanced power factor, reduced lattice thermal conductivity, and therefore improved thermoelectric figure of merit. Most importantly, the band gap of these materials can be tuned between 0.1 eV and 0.5 eV by adjusting the transition metal content, making it possible to design type I clathrates with excellent thermoelectric properties between 500 K and 1000 K.

Apatite, Ca{sub 5}(PO{sub 4}){sub 3}(F,OH,Cl)(P6{sub 3}/m, Z=2), is the most abundant phosphate mineral on Earth. The end-member hydroxyapatite, Ca{sub 5}(PO{sub 4}){sub 3}OH(P2{sub 1}/b), is the primary mineral component in bones and teeth and tends to scavenge and sequester heavy metals in the human body. Hydroxyapatite has also been shown to be effective at sequestering radionuclides and heavy metals in certain natural systems (Dybowska et al., 2004). Hydroxyapatite has been the focus of many laboratory studies and is utilized for environmental remediation of contaminated sites (Moore et al., 2002). The crystal structure of apatite tolerates a great deal of distortion caused by extensive chemical substitutions. Metal cations (e.g. REE, actinides, K, Na, Mn, Ni, Cu, Co, Zn, Sr, Ba, Pb, Cd, Fe) substitute for Ca, and oxyanions (e.g. AsO{sub 4}{sup 3-}, SO{sub 4}{sup 2-}, CO{sub 3}{sup 2-}, SiO{sub 4}{sup 4-}, CrO{sub 4}{sup 2-}) replace PO{sub 4}{sup 3-} through a series of coupled substitutions that preserve electroneutrality. Owing to the ability of apatite to incorporate 'impurities'(including actinides) gives rise to its proposed use as a waste form for radionuclides. Recent work at Sandia National Laboratory demonstrated that hydroxyapatite has a strong affinity for U, Pu, Np, Sr and Tc reduced from pertechnetate (TcO{sub 4}{sup -}) by SnCl{sub 2} (Moore et al., 2002). Based on these earlier promising results, an investigation was initiated into the use of apatite-type materials doped with aliovalent cations including Fe, Cu and Sn as Tc-scavengers. Synthetic Fe and Cu-doped hydroxyapatite samples were prepared by precipitation of Ca, from Ca-acetate, and P, from ammonium phosphate. The Fe and Cu were introduced as chlorides into the Ca-acetate solution. Stannous chloride was used as a reducing agent and was apparently incorporated into the crystal structures of the hydroxyapatite samples in small, as yet undetermined quantities.

Apatite, Ca{sub 5}(PO{sub 4}){sub 3}(F,OH,Cl) (P6{sub 3}/m, Z=2), is the most abundant phosphate mineral on Earth. The end-member hydroxyapatite, Ca{sub 5}(PO{sub 4}){sub 3}OH (P2{sub 1}/b), is the primary mineral component in bones and teeth and tends to scavenge and sequester heavy metals in the human body. Hydroxyapatite has also been shown to be effective at sequestering radionuclides and heavy metals in certain natural systems (Dybowska et al., 2004). Hydroxyapatite has been the focus of many laboratory studies and is utilized for environmental remediation of contaminated sites (Moore et al., 2002). The crystal structure of apatite tolerates a great deal of distortion caused by extensive chemical substitutions. Metal cations (e.g. REE, actinides, K, Na, Mn, Ni, Cu, Co, Zn, Sr, Ba, Pb, Cd, Fe) substitute for Ca, and oxyanions (e.g. AsO{sub 4}{sup 3-}, SO{sub 4}{sup 2-}, CO{sub 3}{sup 2-}, SiO{sub 4}{sup 4-}, CrO{sub 4}{sup 2-}) replace PO{sub 4}{sup 3-} through a series of coupled substitutions that preserve electroneutrality. Owing to the ability of apatite to incorporate ''impurities'' (including actinides) gives rise to its proposed use as a waste form for radionuclides. Recent work at Sandia National Laboratory demonstrated that hydroxyapatite has a strong affinity for U, Pu, Np, Sr and Tc reduced from pertechnetate (TcO{sub 4}{sup -}) by SnCl{sub 2} (Moore et al., 2002). Based on these earlier promising results, an investigation was initiated into the use of apatite-type materials doped with aliovalent cations including Fe, Cu and Sn as Tc-scavengers. Synthetic Fe and Cu-doped hydroxyapatite samples were prepared by precipitation of Ca, from Ca-acetate, and P, from ammonium phosphate. The Fe and Cu were introduced as chlorides into the Ca-acetate solution. Stannous chloride was used as a reducing agent and was apparently incorporated into the crystal structures of the hydroxyapatite samples in small, as yet undetermined quantities.

Dual-modality imaging with magnetic resonance (MR) and upconversion luminescence (UCL) is a promising technique for molecular imaging in biomedical research. Multifunctional lanthanide-based nanoparticles have been widely investigated as agents for contrast enhanced MR and fluorescence imaging. However, the use of rare earth fluoride nanoparticles for dual-modality imaging of T2-weighted MR and UCL is rarely reported. We find that NaYF4:Yb(3+),Tm(3+),Co(2+) (MUC) nanorods can be applied as a high-performance dual contrast agent for both T2-weighted MR and UCL dual-modality imaging. After modification with 6-O-carboxymethyl chitosan (OCC), MUC nanorods can be endocytosed by cells without showing signs of cytotoxicity. High-quality UCL images of living cells incubated with MUC-OCC nanorods were acquired on a near-infrared (NIR) confocal microscopy under the excitation at 980 nm. Moreover, MUC-OCC nanorods display high transverse (r2) relaxivities in vitro. The application of low-dose MUC-OCC nanorods for NIR-to-NIR UCL and MR dual-modality in vivo imaging was also carried out successfully. In addition, the toxicity of MUC-OCC nanorods was evaluated by MTT assay, serological tests and histological analysis of visceral organs.

This paper presents single nanostructure devices as a powerful new diagnostic tool for batteries with LiMn(2)O(4) nanorod materials as an example. LiMn(2)O(4) and Al-doped LiMn(2)O(4) nanorods were synthesized by a two-step method that combines hydrothermal synthesis of beta-MnO(2) nanorods and a solid state reaction to convert them to LiMn(2)O(4) nanorods. lambda-MnO(2) nanorods were also prepared by acid treatment of LiMn(2)O(4) nanorods. The effect of electrolyte etching on these LiMn(2)O(4)-related nanorods is investigated by both SEM and single-nanorod transport measurement, and this is the first time that the transport properties of this material have been studied at the level of an individual single-crystalline particle. Experiments show that Al dopants reduce the dissolution of Mn(3+) ions significantly and make the LiAl(0.1)Mn(1.9)O(4) nanorods much more stable than LiMn(2)O(4) against electrolyte etching, which is reflected by the magnification of both size shrinkage and conductance decrease. These results correlate well with the better cycling performance of Al-doped LiMn(2)O(4) in our Li-ion battery tests: LiAl(0.1)Mn(1.9)O(4) nanorods achieve 96% capacity retention after 100 cycles at 1C rate at room temperature, and 80% at 60 degrees C, whereas LiMn(2)O(4) shows worse retention of 91% at room temperature, and 69% at 60 degrees C. Moreover, temperature-dependent I-V measurements indicate that the sharp electronic resistance increase due to charge ordering transition at 290 K does not appear in our LiMn(2)O(4) nanorod samples, suggesting good battery performance at low temperature.

In this work, systematic study of the formation energy, crystalline and electronic structures of 3d transition metal (Sc, V, Cr, Mn, Fe, Co and Ni) doped anatase TiO2 specimens with and without oxygen vacancy has been carried out by the first principles calculations. The impurity states located at the band gaps enhance the visible light absorption, and the oxygen vacancy result in the EF move into the CB for some doped systems, which induce the Ti3+ ions and promote the separation of photogenerated carriers. Doping and oxygen vacancy can change the hybrid strength and MP value of TMsbnd O bonding which has the approximately linearly with the band gap.

We formulate a scheme to realize a half metallic antiferromagnet (HMAFM), a material conductive in only one spin channel while exhibiting zero macroscopic magnetism, by doping carrier into a class of cuprates. The working rationale is exhibited as taking advantage of Hubbard repulsion of d electrons of Cu atoms and the charge-transfer effect from the associated O ligand to fully polarize the spin of a doped carrier. Specifically, doping one hole into the insulating ferrimagnet Sr8CaRe3Cu4O24 by replacing one of the eight Sr atoms by one Rb atom is predicted to achieve a HMAFM, presumably with room-temperature operation. Since the working rationale is the strong correlations of electrons commonly encountered in cuprates, it is expected that the present findings can shed light on a new way to develop a HMAFM.

Titanium dioxide is a well-known photoactive semiconductor with a variety of possible applications. The procedure of pollutant degradation is mainly performed using TiO2 powder suspension. It can also be exploited an immobilized catalyst on a solid support. Morphology and chemical doping have a great influence on TiO2 activity under illumination. Here we compare photoactivity of titania nanotube arrays doped with non-metal atoms: nitrogen, iodine and boron applied for photodegradation of organic dye - methylene blue and terephtalic acid. The doped samples act as a much better photocatalyst in the degradation process of methylene blue and lead to the formation of much higher amount of hydroxyl radicals (•OH) than undoped TiO2 nanotube arrays. The use of a catalyst active under solar light illumination in the form of thin films on a stable substrate can be scaled up for an industrial application.

Devices composed of transparent materials, particularly those utilizing metal oxides, are of significant interest due to increased demand from industry for higher fidelity transparent thin film transistors, photovoltaics and a myriad of other optoelectronic devices and optics that require more cost-effective and simplified processing techniques for functional oxides and coatings. Here, we report a facile solution processed technique for the formation of a transparent thin film through an inter-diffusion process involving substrate dopant species at a range of low annealing temperatures compatible with processing conditions required by many state-of-the-art devices. The inter-diffusion process facilitates the movement of Si, Na and O species from the substrate into the as-deposited vanadium oxide thin film forming a composite fully transparent V0.0352O0.547Si0.4078Na0.01. Thin film X-ray diffraction and Raman scattering spectroscopy show the crystalline component of the structure to be α-NaVO3 within a glassy matrix. This optical coating exhibits high broadband transparency, exceeding 90-97% absolute transmission across the UV-to-NIR spectral range, while having low roughness and free of surface defects and pinholes. The production of transparent films for advanced optoelectronic devices, optical coatings, and low- or high-k oxides is important for planar or complex shaped optics or surfaces. It provides opportunities for dopingmetal oxides to ternary, quaternary or other mixed metal oxides on glass, encapsulants or other substrates that facilitate diffusional movement of dopant species.Devices composed of transparent materials, particularly those utilizing metal oxides, are of significant interest due to increased demand from industry for higher fidelity transparent thin film transistors, photovoltaics and a myriad of other optoelectronic devices and optics that require more cost-effective and simplified processing techniques for functional oxides and coatings

Devices composed of transparent materials, particularly those utilizing metal oxides, are of significant interest due to increased demand from industry for higher fidelity transparent thin film transistors, photovoltaics and a myriad of other optoelectronic devices and optics that require more cost-effective and simplified processing techniques for functional oxides and coatings. Here, we report a facile solution processed technique for the formation of a transparent thin film through an inter-diffusion process involving substrate dopant species at a range of low annealing temperatures compatible with processing conditions required by many state-of-the-art devices. The inter-diffusion process facilitates the movement of Si, Na and O species from the substrate into the as-deposited vanadium oxide thin film forming a composite fully transparent V0.0352O0.547Si0.4078Na0.01. Thin film X-ray diffraction and Raman scattering spectroscopy show the crystalline component of the structure to be α-NaVO3 within a glassy matrix. This optical coating exhibits high broadband transparency, exceeding 90-97% absolute transmission across the UV-to-NIR spectral range, while having low roughness and free of surface defects and pinholes. The production of transparent films for advanced optoelectronic devices, optical coatings, and low- or high-k oxides is important for planar or complex shaped optics or surfaces. It provides opportunities for dopingmetal oxides to ternary, quaternary or other mixed metal oxides on glass, encapsulants or other substrates that facilitate diffusional movement of dopant species.

Enhanced photocurrent values were achieved through a semiconductor-core/metal-shell nanorod array photoconductive device geometry. Vertically aligned indium sulfide (In2S3) nanorods were formed as the core by using glancing angle deposition technique (GLAD). A thin silver (Ag) layer is conformally coated around nanorods as the metallic shell through a high pressure sputter deposition method. This was followed by capping the nanorods with a metallic blanket layer of Ag film by utilizing a new small angle deposition technique combined with GLAD. Radial interface that was formed by the core/shell geometry provided an efficient charge carrier collection by shortening carrier transit times, which led to a superior photocurrent and gain. Thin metal shells around nanorods acted as a passivation layer to decrease surface states that cause prolonged carrier lifetimes and slow recovery of the photocurrent in nanorods. A combination of efficient carrier collection with surface passivation resulted in enhanced photocurrent and dynamic response at the same time in one device structure. In2S3 nanorod devices without the metal shell and with relatively thicker metal shell were also fabricated and characterized for comparison. In2S3 nanorods with thin metal shell showed the highest photosensitivity (photocurrent/dark current) response compared to two other designs. Microstructural, morphological, and electronic properties of the core/shell nanorods were used to explain the results observed.

We doped PrBa2Cu3O7 (PBCO) using various metals (M) to obtain PrBa2[Cu(1- x)M x ]O7 (PBCMO) ceramic samples and epitaxial thin films. As suggested in the above chemical composition, these samples were made by replacing some of the Cu ions in PBCO with its metallic neighbors (M) such as Al, Co, Fe, Ga, Ni, and Zn at four different doping concentrations ( x)—0.05, 0.10, 0.15, and 0.20. The epitaxial films were made by performing laser ablation on a ceramic disk target. We also present the results of our transport and Raman studies on the aforementioned PBCMO samples. From our Raman data, we were able to identify the doping sites used. Combined with the transport data, this enabled us to explain the abnormal increase in the electrical resistivity of our doped samples. Our transport property studies on PBCMO samples and the YBCO/PBCMO multilayer allowed us to deduce the superconducting coupling length, the finite-size effect, and the two-dimensional phase transition of YBCO.

A systematic method to control the porosity of silicon nanowires is presented. This method is based on metal-assisted chemical etching (MACE) and takes advantage of an HF/H2O2 etching solution and a silver catalyst in the form of a thin patterned film deposited on a doped silicon wafer. It is found that the porosity of the etched nanowires can be controlled by the doping level of the wafer. For low doping concentrations, the wires are primarily crystalline and surrounded by only a very thin layer of porous silicon (pSi) layer, while for highly doped silicon, they are porous in their entire volume. We performed a series of controlled experiments to conclude that there exists a well-defined critical doping concentration separating the crystalline and porous regimes. Furthermore, transmission electron microscopy investigations showed that the pSi has also a crystalline morphology on a length scale smaller than the pore size, determined from positron annihilation lifetime spectroscopy to be mesoscopic. Based on the experimental evidence, we devise a theoretical model of the pSi formation during MACE and apply it for better control of the nanowire morphology.

A systematic method to control the porosity of silicon nanowires is presented. This method is based on metal-assisted chemical etching (MACE) and takes advantage of an HF/H2O2 etching solution and a silver catalyst in the form of a thin patterned film deposited on a doped silicon wafer. It is found that the porosity of the etched nanowires can be controlled by the doping level of the wafer. For low doping concentrations, the wires are primarily crystalline and surrounded by only a very thin layer of porous silicon (pSi) layer, while for highly doped silicon, they are porous in their entire volume. We performed a series of controlled experiments to conclude that there exists a well-defined critical doping concentration separating the crystalline and porous regimes. Furthermore, transmission electron microscopy investigations showed that the pSi has also a crystalline morphology on a length scale smaller than the pore size, determined from positron annihilation lifetime spectroscopy to be mesoscopic. Based on the experimental evidence, we devise a theoretical model of the pSi formation during MACE and apply it for better control of the nanowire morphology.

Andreev conductance across a normal metal-superconductor (N-S) junction of doped correlated quantum spin Hall insulator on honeycomb lattice is theoretically studied via Blonder-Tinkham-Klapwijk (BTK) formalism. The normal side is modeled by the doped Kane-Mele (KM) model. The superconducting side is a doped correlated KM t-J model, which has been shown to feature d+id'-wave spin singlet pairing. With increasing intrinsic spin-orbit coupling, the doped KM t-J system undergoes a topological phase transition from the chiral d-wave superconductivity to the Z2 spin-Chern superconducting phase with helical Majorana fermions at edges. We apply a local strain on the N-S interface to generate an effective Dirac-delta barrier and study the transport near the chiral-helical phase transition in the weak tunneling limit. We explore the Andreev conductance at the K and K' Dirac points, respectively and find the distinctive behaviors across the transition. Relevance of our results for the adatom-doped graphene is discussed. Reference: S.J. Sun, C.H. Chung, Y.Y. Chang, W.F. Tsai, and F.C. Zhang, arXiv:1506.02584.'' Y.Y. C. acknowledges the support from the MOST Grant No.104-2112-M-009-004-MY3 and the NCTS of Taiwan, R.O.C.

Spin polarized density functional calculations were employed to study chirality effect on electronic and magnetic properties of 3d transition metals (TMs) endo-doped co-diameter (∼7 Å) narrow (5,5) and (9,0) single walled carbon nanotubes (CNTs). Various magnetizations up to ∼6μB was obtained for different 3dTM-CNT systems (recall that the magnetization of fcc structure cobalt is ∼1.6μB). In addition nearly half-metallic magnetic behavior has been observed for the most of considered systems. These results would be useful for spintronic and nano-magnetic technology.

The ongoing search for new non-precious-metal catalysts (NPMCs) with excellent electrocatalytic performance to replace Pt-based catalysts has been viewed as an important strategy to promote the development of fuel cells. Recent studies have proven that carbon materials doped with atoms which have a relatively small atomic size (e.g. N, B, P or S), have also shown pronounced catalytic activity. Herein, we demonstrate the successful fabrication of CNT/graphene doped with Se atoms, which has a relatively large atomic size, by a simple, economical, and scalable approach. The electrocatalytic performance of the resulting Se-doped CNT-graphene catalyst exhibits excellent catalytic activity, long-term stability, and a high methanol tolerance compared to commercial Pt/C catalysts. Our results confirmed that combining CNTs with graphene is an effective strategy to synergistically improve ORR activity. More importantly, it is also suggested that the development of graphite materials doped with Se or other heteroatoms of large size will open up a new route to obtain ideal NPMCs with realistic value for fuel cell applications.The ongoing search for new non-precious-metal catalysts (NPMCs) with excellent electrocatalytic performance to replace Pt-based catalysts has been viewed as an important strategy to promote the development of fuel cells. Recent studies have proven that carbon materials doped with atoms which have a relatively small atomic size (e.g. N, B, P or S), have also shown pronounced catalytic activity. Herein, we demonstrate the successful fabrication of CNT/graphene doped with Se atoms, which has a relatively large atomic size, by a simple, economical, and scalable approach. The electrocatalytic performance of the resulting Se-doped CNT-graphene catalyst exhibits excellent catalytic activity, long-term stability, and a high methanol tolerance compared to commercial Pt/C catalysts. Our results confirmed that combining CNTs with graphene is an effective strategy to

Oxygen reduction reaction (ORR) is an important reaction in energy conversion systems such as fuel cells and metal-air batteries. Carbon nanomaterials doped with heteroatoms are highly attractive materials for use as electrocatalysts by virtue of their excellent electrocatalytic activity, high conductivity, and large surface area. This study reports the synthesis of highly efficient electrocatalysts based on heteroatom-doped graphene nanosheets prepared through covalent functionalization using various small organic molecules and a subsequent thermal treatment. A series of nitrogen-doped reduced graphene oxide (NRGOn) nanosheets exhibited varying degrees and configurations of nitrogen atoms within the graphitic framework depending on the type of precursors used. On the basis of the rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) experiments, NRGO3, with a high degree of pyridinic-N content, displayed the desired one-step, quasi-four-electron transfer pathway during ORR, similar to commercial Pt/C. We also demonstrated the potential of covalent functionalization of sulfur and boron-doped graphene nanosheets.Oxygen reduction reaction (ORR) is an important reaction in energy conversion systems such as fuel cells and metal-air batteries. Carbon nanomaterials doped with heteroatoms are highly attractive materials for use as electrocatalysts by virtue of their excellent electrocatalytic activity, high conductivity, and large surface area. This study reports the synthesis of highly efficient electrocatalysts based on heteroatom-doped graphene nanosheets prepared through covalent functionalization using various small organic molecules and a subsequent thermal treatment. A series of nitrogen-doped reduced graphene oxide (NRGOn) nanosheets exhibited varying degrees and configurations of nitrogen atoms within the graphitic framework depending on the type of precursors used. On the basis of the rotating disk electrode (RDE) and rotating ring-disk electrode

Lead free solders currently in use are prone to develop thick interfacial intermetallic compound layers with rough morphology which are detrimental to the long term solder joint reliability. A novel method has been developed to control the morphology and growth of intermetallic compound layers between lead-free Sn–3.0Ag–0.5Cu solder ball and copper substrate by doping a water soluble flux with metallic nanoparticles. Four types of metallic nanoparticles (nickel, cobalt, molybdenum and titanium) were used to investigate their effects on the wetting behavior and interfacial microstructural evaluations after reflow. Nanoparticles were dispersed manually with a water soluble flux and the resulting nanoparticle doped flux was placed on copper substrate. Lead-free Sn–3.0Ag–0.5Cu solder balls of diameter 0.45 mm were placed on top of the flux and were reflowed at a peak temperature of 240 °C for 45 s. Angle of contact, wetting area and interfacial microstructure were studied by optical microscopy, field emission scanning electron microscopy and energy-dispersive X-ray spectroscopy. It was observed that the angle of contact increased and wetting area decreased with the addition of cobalt, molybdenum and titanium nanoparticles to flux. On the other hand, wettability improved with the addition of nickel nanoparticles. Cross-sectional micrographs revealed that both nickel and cobalt nanoparticle doping transformed the morphology of Cu{sub 6}Sn{sub 5} from a typical scallop type to a planer one and reduced the intermetallic compound thickness under optimum condition. These effects were suggested to be related to in-situ interfacial alloying at the interface during reflow. The minimum amount of nanoparticles required to produce the planer morphology was found to be 0.1 wt.% for both nickel and cobalt. Molybdenum and titanium nanoparticles neither appear to undergo alloying during reflow nor have any influence at the solder/substrate interfacial reaction. Thus, doping

Since the graphitic carbon nitride (g-C4N3), which can be seen as C-doped graphitic-C3N4 (g-C3N4), was reported to display ferromagnetic ground state and intrinsic half-metallicity (Du et al., PRL,108,197207,2012), it has attracted numerous research interest to tune the electronic structure and magnetic properties of g-C3N4 due to their potential applications in spintronic devices. In this paper, we reported the experimentally achieving of high temperature ferromagnetism in metal-free ultrathin g-C3N4 nanosheets by introducing of B atoms. Further, first-principles calculation results revealed that the current flow in such a system was fully spin-polarized and the magnetic moment was mainly attributed to the p orbital of N atoms in B doped g-C3N4 monolayer, giving the theoretic evidence of the ferromagnetism and half-metallicity. Our finding provided a new perspective for B doped g-C3N4 spintronic devices in future. PMID:27762348

Since the graphitic carbon nitride (g-C4N3), which can be seen as C-doped graphitic-C3N4 (g-C3N4), was reported to display ferromagnetic ground state and intrinsic half-metallicity (Du et al., PRL,108,197207,2012), it has attracted numerous research interest to tune the electronic structure and magnetic properties of g-C3N4 due to their potential applications in spintronic devices. In this paper, we reported the experimentally achieving of high temperature ferromagnetism in metal-free ultrathin g-C3N4 nanosheets by introducing of B atoms. Further, first-principles calculation results revealed that the current flow in such a system was fully spin-polarized and the magnetic moment was mainly attributed to the p orbital of N atoms in B doped g-C3N4 monolayer, giving the theoretic evidence of the ferromagnetism and half-metallicity. Our finding provided a new perspective for B doped g-C3N4 spintronic devices in future.

Since the graphitic carbon nitride (g-C4N3), which can be seen as C-doped graphitic-C3N4 (g-C3N4), was reported to display ferromagnetic ground state and intrinsic half-metallicity (Du et al., PRL,108,197207,2012), it has attracted numerous research interest to tune the electronic structure and magnetic properties of g-C3N4 due to their potential applications in spintronic devices. In this paper, we reported the experimentally achieving of high temperature ferromagnetism in metal-free ultrathin g-C3N4 nanosheets by introducing of B atoms. Further, first-principles calculation results revealed that the current flow in such a system was fully spin-polarized and the magnetic moment was mainly attributed to the p orbital of N atoms in B doped g-C3N4 monolayer, giving the theoretic evidence of the ferromagnetism and half-metallicity. Our finding provided a new perspective for B doped g-C3N4 spintronic devices in future.

Lanthanide and transition metaldoped hexagonal beta-NaYF4 nanocrystals have a wide variety of applications in bioimaging, solar concentrators, display panel technology, photodynamic therapy, and security printing. This dissertation research employed two complementary approaches to characterizing the photoactive properties of lanthanides and transition metalsdoped in beta-NaYF 4. One approach was a semi-empirical method, based on Judd-Ofelt theory, used to calculate the optical transition intensity parameters for Er 3+ doped in beta-phase NaYF4:Yb3+ from measured emission intensity ratios and the diffuse reflectance spectrum. The second approach was based on first-principles density functional theory, investigating the effect of doping on the electronic structure of the materials of interest. In this latter approach, models of beta-NaYF4 with different numbers of atoms in supercells were built, where supercells were reproduced through translational symmetry creating periodic boundary conditions. The models were tested for convergence of local structure and energy as a function of supercell size. First, a converged model for the un-doped "parent" structure of the host material was developed using the Perdew-Burke-Ernzerhof (PBE) functional. Then, a systematic investigation of the optimized geometry and electronic structure of the doped beta-NaYF4: Ln3+ nanocrystals, was conducted using both spin-polarized DFT and non-collinear-spin DFT. For transition metaldoping, the relationship between site symmetry and spin state with different doping concentrations was also demonstrated.

A method of hydrogenation utilizing a reactant gas mixture comprising a carbon oxide and a hydrogen agent, and a hydrogenation catalyst comprising a mixed-metal oxide containing metal sites supported and/or incorporated into the lattice. The mixed-metal oxide comprises a perovskite, a pyrochlore, a fluorite, a brownmillerite, or mixtures thereof doped at the A-site or the B-site. The metal site may comprise a deposited metal, where the deposited metal is a transition metal, an alkali metal, an alkaline earth metal, or mixtures thereof. Contact between the carbon oxide, hydrogen agent, and hydrogenation catalyst under appropriate conditions of temperature, pressure and gas flow rate generate a hydrogenation reaction and produce a hydrogenated product made up of carbon from the carbon oxide and some portion of the hydrogen agent. The carbon oxide may be CO, CO.sub.2, or mixtures thereof and the hydrogen agent may be H.sub.2. In a particular embodiment, the hydrogenated product comprises an alcohol, an olefin, an aldehyde, a ketone, an ester, an oxo-product, or mixtures thereof.

A method of hydrogenation utilizing a reactant gas mixture comprising a carbon oxide and a hydrogen agent, and a hydrogenation catalyst comprising a mixed-metal oxide containing metal sites supported and/or incorporated into the lattice. The mixed-metal oxide comprises a pyrochlore, a brownmillerite, or mixtures thereof doped at the A-site or the B-site. The metal site may comprise a deposited metal, where the deposited metal is a transition metal, an alkali metal, an alkaline earth metal, or mixtures thereof. Contact between the carbon oxide, hydrogen agent, and hydrogenation catalyst under appropriate conditions of temperature, pressure and gas flow rate generate a hydrogenation reaction and produce a hydrogenated product made up of carbon from the carbon oxide and some portion of the hydrogen agent. The carbon oxide may be CO, CO.sub.2, or mixtures thereof and the hydrogen agent may be H.sub.2. In a particular embodiment, the hydrogenated product comprises olefins, paraffins, or mixtures thereof.

The full potential linear augmented plane wave (FPLAPW) based on density-functional theory (DFT) is employed to study the structural, electronic and magnetic properties of transition metal Co doped CdTe. We have analyzed the structural parameters, charge and spin densities, total and partial densities of states within the generalized gradient approximation (GGA). The results show a Half-Metallic Dilute Magnetic Semiconductors (HM-DMS) character with an important magnetic moment. The results obtained, make the CoxCd1-xTe a potential promising candidate for application in spintronics.

The optical and electrical properties of doped solution-deposited and rf sputter-deposited thin metal oxide films were investigated following post deposition pulsed laser irradiation. Solution deposited films were annealed at 450 ºC. Following the heating regiment, the transparent metal oxide films were subjected to 355 nm pulsed Nd:YAG laser irradiation (4 nsec pulsewidth) at fluences between 5 and 150 mJ/cm2. Irradiation times at pulse frequencies of 30 Hz ranged from seconds to tens of minutes. Film densification, index change and a marked increase in conductivity were observed following irradiation in air and under vacuum of Al:ZnO (AZO), Ga:ZnO (GZO), and In:ZnO (IZO) films deposited on silica substrates. Despite the measured increase in conductivity, all films continued to show high transparency on the order of 90% at wavelengths from the band edge well into the near infrared region of the spectrum. Laser energies required for turning on the conductivity of these films varied depending upon the dopant. Irradiations in air yielded resistivity measurements on the order of 16.cm. Resistivities of films irradiated under vacuum were on the order of 0.1.cm. The increase in conductivity can be attributed to the formation of oxygen vacancies and subsequent promotion of free carriers into the conduction band. All irradiated films become insulating after around 24 hours. Oxygen atoms in air become reduced by electrons in the metal conduction band and diffuse into the vacancies in the lattice. The rate of this reduction process depends on the type of dopant. This work also sheds light on the damage threshold, correlating the optical properties with the presence of free carriers that have been introduced into the conduction band. All films were characterized by means of UV-VIS-NIR transmission spectroscopy, visible and UV Raman spectroscopy and Hall measurements. Analysis of interference fringes in measured transmission spectra allowed film density and refractive index

To promote the oxygen reduction reaction of metal-free catalysts, the introduction of porous structure is considered as a desirable approach because the structure can enhance mass transport and host many catalytic active sites. However, most of the previous studies reported only half-cell characterization; therefore, studies on membrane electrode assembly (MEA) are still insufficient. Furthermore, the effect of doping-site position in the structure has not been investigated. Here, we report the synthesis of highly active metal-free catalysts in MEAs by controlling pore size and doping-site position. Both influence the accessibility of reactants to doping sites, which affects utilization of doping sites and mass-transport properties. Finally, an N,P-codoped ordered mesoporous carbon with a large pore size and precisely controlled doping-site position showed a remarkable on-set potential and produced 70% of the maximum power density obtained using Pt/C.

The electrocatalytic properties of metal oxides (MO = Fe3O4, ZnO) nanoparticles doped phthalocyanine (Pc) and functionalized MWCNTs, decorated on glassy carbon electrode (GCE) was investigated. Successful synthesis of the metal oxide nanoparticles and the MO/Pc/MWCNT composite were confirmed using UV-Vis, EDX, XRD and TEM techniques. Successful modification of GCE with the MO and their composite was also confirmed using cyclic voltammetry (CV) technique. GCE-MWCNT/ZnO/29H,31H-Pc was the best electrode towards DA detection with very low detection limit (0.75 μM) which compared favourably with literature, good sensitivity (1.45 μA/μM), resistance to electrode fouling, and excellent ability to detect DA without interference from AA signal. Electrocatalytic oxidation of DA on GCE-MWCNT/ZnO/29H,31H-Pc electrode was diffusion controlled but characterized with some adsorption of electro-oxidation reaction intermediates products. The fabricated sensors are easy to prepare, cost effective and can be applied for real sample analysis of dopamine in drug composition. The good electrocatalytic properties of 29H,31H-Pc and 2,3-Nc were related to their (quantum chemically derived) frontier molecular orbital energies and global electronegativities. The better performance of 29H,31H-Pc than 2,3-Nc in aiding electrochemical oxidation of DA might be due to its better electron accepting ability, which is inferred from its lower ELUMO and higher χ. PMID:28256521

Glassy carbon electrode (GCE) was modified with metal oxides (MO = Fe3O4, ZnO) nanoparticles doped phthalocyanine (Pc) and functionalized MWCNTs, and the electrocatalytic properties were studied. Successful synthesis of the metal oxide nanoparticles and the MO/Pc/MWCNT composite were confirmed using FTIR, Raman and SEM techniques. The electrodes were characterized using cyclic voltammetry (CV) technique. The electrocatalytic behaviour of the electrode towards epinephrine (EP) and norepinephrine (NE) oxidation was investigated using CV and DPV. Result showed that GCE-MWCNT/Fe3O4/2,3-Nc, GCE-MWCNT/Fe3O429H,31H-Pc, GCE-MWCNT/ZnO/2,3-Nc and GCE-MWCNT/ZnO/29H,31H-Pc electrodes gave enhanced EP and NE current response. Stability study indicated that the four GCE-MWCNT/MO/Pc modified electrodes were stable against electrode fouling effect with the percentage NE current drop of 5.56–5.88% after 20 scans. GCE-MWCNT/Fe3O4/29H,31H-Pc gave the lowest limit of detection (4.6 μM) towards EP while MWCNT/ZnO/29H,31H-Pc gave the lowest limit of detection (1.7 μM) towards NE. The limit of detection and sensitivity of the electrodes compared well with literature. Electrocatalytic oxidation of EP and NE on GCE-MWCNT/MO/Pc electrodes was diffusion controlled with some adsorption of electro-oxidation reaction intermediates products. The electrodes were found to be electrochemically stable, reusable and can be used for the analysis of EP and NE in real life samples.

Metal organic complexes, diaceto bis benzimidazole cobalt(II) and diaceto bis benzimidazole copper(II), are synthesized by a simple chemical route. The synthesized powders are doped in PMMA with 1, 3, 5 wt% and deposited as free standing films of thickness ∼1 μm. For theoretical simulation, metal organic complex (MOC) embedded into the PMMA matrix is subjected to polarizability and hyperpolarizability calculations using the PM6 algorithm in MOPAC2012 package. It is found that the minimum interaction distance between PMMA and MOC is about 34 nm and does not vary with respect to the dopant. The copper complex shows higher interaction energy with the polymer matrix than the cobalt complex. Time dependent Hartree Fock approach is used to calculate the α, β and γ values for static, 0.25 and 0.5 eV energies; the cobalt complex shows higher polarizability and hyperpolarizability than the copper complex. Experimentally, the optical absorption, thermo-optic coefficient, nonlinear absorption coefficient and nonlinear refractive index of the samples are determined. The thermo-optic coefficients of the samples are seen to increase with increasing dopant concentration. From open aperture Z-scan studies the films are found to exhibit reverse saturable absorption behaviour, and from the closed aperture Z-scan all samples are found to exhibit self-focusing effects. The calculated third order susceptibility is in the order of 10‑5 esu. The optical limiting properties are studied at 650 nm using a 20 mW laser and all the samples are found to exhibit good optical limiting in the operating wavelength.

A thermoelectric material includes a multiple transition metal-doped type I clathrate crystal structure having the formula A.sub.8TM.sub.y.sub.1.sup.1TM.sub.y.sub.2.sup.2 . . . TM.sub.y.sub.n.sup.nM.sub.zX.sub.46-y.sub.1.sub.-y.sub.2.sub.- . . . -y.sub.n.sub.-z. In the formula, A is selected from the group consisting of barium, strontium, and europium; X is selected from the group consisting of silicon, germanium, and tin; M is selected from the group consisting of aluminum, gallium, and indium; TM.sup.1, TM.sup.2, and TM.sup.n are independently selected from the group consisting of 3d, 4d, and 5d transition metals; and y.sub.1, y.sub.2, y.sub.n and Z are actual compositions of TM.sup.1, TM.sup.2, TM.sup.n, and M, respectively. The actual compositions are based upon nominal compositions derived from the following equation: z=8q.sub.A-|.DELTA.q.sub.1|y.sub.1-|.DELTA.q.sub.2|y.sub.2- . . . -|.DELTA.q.sub.n|y.sub.n, wherein q.sub.A is a charge state of A, and wherein .DELTA.q.sub.1, .DELTA.q.sub.2, .DELTA.q.sub.n are, respectively, the nominal charge state of the first, second, and n-th TM.

Glassy carbon electrode (GCE) was modified with metal oxides (MO = Fe3O4, ZnO) nanoparticles doped phthalocyanine (Pc) and functionalized MWCNTs, and the electrocatalytic properties were studied. Successful synthesis of the metal oxide nanoparticles and the MO/Pc/MWCNT composite were confirmed using FTIR, Raman and SEM techniques. The electrodes were characterized using cyclic voltammetry (CV) technique. The electrocatalytic behaviour of the electrode towards epinephrine (EP) and norepinephrine (NE) oxidation was investigated using CV and DPV. Result showed that GCE-MWCNT/Fe3O4/2,3-Nc, GCE-MWCNT/Fe3O429H,31H-Pc, GCE-MWCNT/ZnO/2,3-Nc and GCE-MWCNT/ZnO/29H,31H-Pc electrodes gave enhanced EP and NE current response. Stability study indicated that the four GCE-MWCNT/MO/Pc modified electrodes were stable against electrode fouling effect with the percentage NE current drop of 5.56–5.88% after 20 scans. GCE-MWCNT/Fe3O4/29H,31H-Pc gave the lowest limit of detection (4.6 μM) towards EP while MWCNT/ZnO/29H,31H-Pc gave the lowest limit of detection (1.7 μM) towards NE. The limit of detection and sensitivity of the electrodes compared well with literature. Electrocatalytic oxidation of EP and NE on GCE-MWCNT/MO/Pc electrodes was diffusion controlled with some adsorption of electro-oxidation reaction intermediates products. The electrodes were found to be electrochemically stable, reusable and can be used for the analysis of EP and NE in real life samples. PMID:27245690

The electrocatalytic properties of metal oxides (MO = Fe3O4, ZnO) nanoparticles doped phthalocyanine (Pc) and functionalized MWCNTs, decorated on glassy carbon electrode (GCE) was investigated. Successful synthesis of the metal oxide nanoparticles and the MO/Pc/MWCNT composite were confirmed using UV-Vis, EDX, XRD and TEM techniques. Successful modification of GCE with the MO and their composite was also confirmed using cyclic voltammetry (CV) technique. GCE-MWCNT/ZnO/29H,31H-Pc was the best electrode towards DA detection with very low detection limit (0.75 μM) which compared favourably with literature, good sensitivity (1.45 μA/μM), resistance to electrode fouling, and excellent ability to detect DA without interference from AA signal. Electrocatalytic oxidation of DA on GCE-MWCNT/ZnO/29H,31H-Pc electrode was diffusion controlled but characterized with some adsorption of electro-oxidation reaction intermediates products. The fabricated sensors are easy to prepare, cost effective and can be applied for real sample analysis of dopamine in drug composition. The good electrocatalytic properties of 29H,31H-Pc and 2,3-Nc were related to their (quantum chemically derived) frontier molecular orbital energies and global electronegativities. The better performance of 29H,31H-Pc than 2,3-Nc in aiding electrochemical oxidation of DA might be due to its better electron accepting ability, which is inferred from its lower ELUMO and higher χ.

The electrocatalytic properties of metal oxides (MO = Fe3O4, ZnO) nanoparticles doped phthalocyanine (Pc) and functionalized MWCNTs, decorated on glassy carbon electrode (GCE) was investigated. Successful synthesis of the metal oxide nanoparticles and the MO/Pc/MWCNT composite were confirmed using UV-Vis, EDX, XRD and TEM techniques. Successful modification of GCE with the MO and their composite was also confirmed using cyclic voltammetry (CV) technique. GCE-MWCNT/ZnO/29H,31H-Pc was the best electrode towards DA detection with very low detection limit (0.75 μM) which compared favourably with literature, good sensitivity (1.45 μA/μM), resistance to electrode fouling, and excellent ability to detect DA without interference from AA signal. Electrocatalytic oxidation of DA on GCE-MWCNT/ZnO/29H,31H-Pc electrode was diffusion controlled but characterized with some adsorption of electro-oxidation reaction intermediates products. The fabricated sensors are easy to prepare, cost effective and can be applied for real sample analysis of dopamine in drug composition. The good electrocatalytic properties of 29H,31H-Pc and 2,3-Nc were related to their (quantum chemically derived) frontier molecular orbital energies and global electronegativities. The better performance of 29H,31H-Pc than 2,3-Nc in aiding electrochemical oxidation of DA might be due to its better electron accepting ability, which is inferred from its lower ELUMO and higher χ.

A systematic investigation was carried out on the material and electrical properties of metal oxide doped germanium dioxide (M-GeO{sub 2}) on Ge. We propose two criteria on the selection of desirable M-GeO{sub 2} for gate stack formation on Ge. First, metal oxides with larger cation radii show stronger ability in modifying GeO{sub 2} network, benefiting the thermal stability and water resistance in M-GeO{sub 2}/Ge stacks. Second, metal oxides with a positive Gibbs free energy for germanidation are required for good interface properties of M-GeO{sub 2}/Ge stacks in terms of preventing the Ge-M metallic bond formation. Aggressive equivalent oxide thickness scaling to 0.5 nm is also demonstrated based on these understandings.

Label-free plasmonic biosensors rely either on surface plasmon polaritons or on localized surface plasmons on continuous or nanostructured noble-metal surfaces to detect molecular-binding events. Despite undisputed advantages, including spectral tunability, strong enhancement of the local electric field and much better adaptability to modern nanobiotechnology architectures, localized plasmons demonstrate orders of magnitude lower sensitivity compared with their guided counterparts. Here, we demonstrate an improvement in biosensing technology using a plasmonic metamaterial that is capable of supporting a guided mode in a porous nanorod layer. Benefiting from a substantial overlap between the probing field and the active biological substance incorporated between the nanorods and a strong plasmon-mediated energy confinement inside the layer, this metamaterial provides an enhanced sensitivity to refractive-index variations of the medium between the rods (more than 30,000nm per refractive-index unit). We demonstrate the feasibility of our approach using a standard streptavidin-biotin affinity model and record considerable improvement in the detection limit of small analytes compared with conventional label-free plasmonic devices.

Density-functional calculations are carried out to understand and tailor the electrochemical profile—diffusivity, band gap, and open-circuit voltage—of transition-metal-doped olivine phosphate: LiFe1 -xMxPO4 (M =V , Cr, Mn, Co, and Ni). Diffusion and, hence, the ionic conductivity is studied by calculating the activation barrier Vact experienced by the diffusing Li+ ion. We show that the effect of dopants on diffusion is both site dependent and short ranged, and thereby it paves ways for microscopic control of ionic conductivity via selective dopants in olivine phosphates. Dopants with lower-valence electrons (LVEs) compared to Fe repel the Li+ ion to facilitate its outward diffusion, whereas higher-valence-electron (HVE) dopants attract the Li+ ion to facilitate the inward diffusion. From the electronic structure calculation, we establish that irrespective of the dopant M , except Mn, the band gap is reduced since the M d states always lie within the pure band gap. Atomically localized d states of HVE dopants lie above the Fermi energy and that of LVE lie below it. Half-filled Mn d states undergo a large spin-exchange split to bury the dopant states in the valence and conduction bands of the pristine system, and, in turn, the band gap remains unchanged in LiFe1 -xMnxPO4 . Baring Mn, the open-circuit voltage increases with HVE dopants and decreases with LVE dopants.

Metal Organic Frameworks (MOFs) are mesoporous materials that can be treated as potential hosts for trapping guest molecules in their pores. Ion conduction and phase behavior dynamics of Ionic Liquids (ILs) can be controlled by tunable interactions of MOFs with the ILs. MOFs incorporated with ionic liquid can be dispersed in the polymers to synthesize polymer electrolyte nanocomposites with high ionic conductivity, electrochemical and thermal stability for applications in energy storage and conversion devices such as rechargeable Li-ion batteries. In the present work we have synthesized Cu-based MOF [Cu3(l,3,5-benzene tricarboxylate)2(H2O)] incorporated with the ionic liquid 1-Butyl-3-methylimidazolium bromide at different weight ratios of MOF and IL. The synthesized MOF-IL composites are dispersed in Poly (ethylene oxide) (PEO). Frequency dependent behavior of permittivity and dielectric loss of the nanocomposites depict the non-Debye dielectric relaxation mechanism. The room temperature Nyquist plots reveal decreasing bulk resistance upto 189 Ω with optimum ionic conductivity of 1.3×10-3S cm-1at maximum doping concentration of IL in the nanocomposite system.

The magnetic properties and clustering behaviors of the transition-metal (TM)-doped ZnO have been studied by first-principles calculations. We demonstrate the relationship between the types of TM (Co, Fe, Ni, and Cu) pairs and the energetic most stable configurations in ZnO:TM. Further calculations show that Co pairs have no tendency to form clusters, showing paramagnetic (PM) state in ZnO:Co samples in an equilibrium state and without excessive defects, as evidenced by various experiments, while ferromagnetic (FM) state is possible for the samples prepared under non-equilibrium conditions. Finally, systematical studies of a series of TM elements reveal different types of TM pairs in terms of clustering behaviors determined by spin-polarized and non-spin-polarized contributions: Co pairs and Fe pairs have no tendency to form clusters, showing PM and FM states, respectively, while Ni pairs and Cu pairs have a clustering tendency and show intrinsic FM ordering.

Titanium dioxide (TiO2) nanorod arrays grown directly on Ti metal foil were prepared by a facile one-step hydrothermal method, in which the Ti foil serves as both substrate and precursor. The nanorods are tetragonal rutile single crystal with growth orientation along the [001] direction. The electrochemical properties of the TiO2 nanorod arrays were systematically investigated by cyclic voltammetry, galvanostatic charge/discharge and electrochemical impedance spectroscopy using a three-electrode system. As a result, the TiO2 nanorod arrays exhibit good areal specific capacitance and excellent cyclic stability by retaining more than 98% of the initial specific capacitance after 1000 cycles. In addition, a good flexibility of the Ti foil with TiO2 nanorod arrays was demonstrated by the stable electrochemical performance under different bending angles, which indicates that TiO2 nanorod arrays grown on Ti foil could be a promising electrode material for flexible supercapacitor application.

An effective strategy to overcome the morphology evolution of hematite nanorods under high-temperature activation is presented, via tuning the crystallinity and sintering temperature by substrate modification. It is demonstrated that the as-prepared doping-free hematite nanorods with fine nanostructures obtain a significantly higher photocurrent density of 2.12 mA cm(-2) at 1.23 V versus RHE, due to effective charge separation and transfer.

The nonlinear optical (NLO) properties of metallic nanoparticles strongly depend on their size and shape. Metallic gold nanorods have already been widely investigated, but other noble metals could also be used for nanorod fabrication towards applications in photonics. Here we report on the synthesis and NLO characterization of silver nanorods (AgNRs) with controllable localized surface plasmon resonance. We have implemented an original, one-step and seedless synthesis method, based on a spontaneous particle growth technique in the presence of polyvinylpyrrolidone (PVP) as a capping agent. Colloidal solutions of AgNRs with various aspect ratios (5.0; 6.3; 7.5; 8.2 and 9.7) have been obtained and characterized using Harmonic light scattering (HLS) at 1064 nm, in order to investigate their quadratic NLO properties. From HLS experiments, we demonstrate that hyperpolarizability (β) values of AgNRs display a strong dependence on their surface area.

Catalytically competent Ir, Re, and Ru complexes H(2)L(1)-H(2)L(6) with dicarboxylic acid functionalities were incorporated into a highly stable and porous Zr(6)O(4)(OH)(4)(bpdc)(6) (UiO-67, bpdc = para-biphenyldicarboxylic acid) framework using a mix-and-match synthetic strategy. The matching ligand lengths between bpdc and L(1)-L(6) ligands allowed the construction of highly crystalline UiO-67 frameworks (metal-organic frameworks (MOFs) 1-6) that were doped with L(1)-L(6) ligands. MOFs 1-6 were isostructural to the parent UiO-67 framework as shown by powder X-ray diffraction (PXRD) and exhibited high surface areas ranging from 1092 to 1497 m(2)/g. MOFs 1-6 were stable in air up to 400 °C and active catalysts in a range of reactions that are relevant to solar energy utilization. MOFs 1-3 containing [Cp*Ir(III)(dcppy)Cl] (H(2)L(1)), [Cp*Ir(III)(dcbpy)Cl]Cl (H(2)L(2)), and [Ir(III)(dcppy)(2)(H(2)O)(2)]OTf (H(2)L(3)) (where Cp* is pentamethylcyclopentadienyl, dcppy is 2-phenylpyridine-5,4'-dicarboxylic acid, and dcbpy is 2,2'-bipyridine-5,5'-dicarboxylic acid) were effective water oxidation catalysts (WOCs), with turnover frequencies (TOFs) of up to 4.8 h(-1). The [Re(I)(CO)(3)(dcbpy)Cl] (H(2)L(4)) derivatized MOF 4 served as an active catalyst for photocatalytic CO(2) reduction with a total turnover number (TON) of 10.9, three times higher than that of the homogeneous complex H(2)L(4). MOFs 5 and 6 contained phosphorescent [Ir(III)(ppy)(2)(dcbpy)]Cl (H(2)L(5)) and [Ru(II)(bpy)(2)(dcbpy)]Cl(2) (H(2)L(6)) (where ppy is 2-phenylpyridine and bpy is 2,2'-bipyridine) and were used in three photocatalytic organic transformations (aza-Henry reaction, aerobic amine coupling, and aerobic oxidation of thioanisole) with very high activities. The inactivity of the parent UiO-67 framework and the reaction supernatants in catalytic water oxidation, CO(2) reduction, and organic transformations indicate both the molecular origin and heterogeneous nature of these catalytic processes

Middle-infrared lasers operating over a "molecular fingerprint" 2-15 mum spectral range are in great demand for a variety of applications. One of the best choices for lasing in the 2-5 mum spectral range is direct oscillation from divalent transition metal ions (TM2+: Cr 2+, Fe2+, Co2+)-doped wide bandgap II-VI semiconductor crystals. There are three major objectives in this dissertation: (1) Realize and study middle-infrared electroluminescence of n and p-type, Cr doped bulk ZnSe crystals. We have demonstrated a method of ZnSe crystals thermal-diffusion doping with donor (In, Zn, and Al) and acceptor (Cu, Ag, and N through CrN) impurities resulting in n and p-type conductivity of Cr:ZnSe. We are the first to our knowledge to obtain mid-IR electroluminescence in nominally p-type Cr:Ag:ZnSe, which could prove valuable for developing of novel mid-IR laser diodes. (2) En route to low dimensional gain material, develop simple method for making microscopic laser active Cr doped ZnSe, ZnS and CdSe powders, realize and study their laser spectroscopic characteristics. We have demonstrated a simple physical method of Cr2+:ZnSe, ZnS and CdSe powder fabrication with average sizes below ˜ 10mum and ˜1mum (eliminating stage of bulk crystal growth) and demonstrated first ever mid-IR random lasing on these powders under optical excitation. In addition, we have examine suspensions and polymer films impregnated with Cr:II-VI powders for random lasing in the mid-IR. The powder, suspension and polymer samples are fabricated and characterized through the measurement of photoluminescence (PL) spectra, PL kinetics, and lasing threshold energy. (3) En route to low dimensional gain material, develop method for making laser active Cr, Co, and Fe doped ZnSe and ZnS quantum dots (QD), realize and study their laser spectroscopic characteristics. We have demonstrated a novel method of TM doped II-VI QDs fabrication based on laser ablation in liquid and Ar environment. TM doped II-VI QDs

Semiconductor TiO2 photocatalysis has attracted much attention due to its potential application in solving the problems of environmental pollution. In this paper, thiourea (CH4N2S) modified anatase TiO2 nanorods were fabricated by calcination of the mixture of TiO2 nanorods and thiourea at 600 °C for 2 h. It was found that only N element was doped into the lattice of TiO2 nanorods. With increasing the weight ratio of thiourea to TiO2 (R) from 0 to 8, the light-harvesting ability of the photocatalyst steady increases. Both the crystallization and photocatalytic activity of TiO2 nanorods increase first and then decrease with increase in R value, and R2 sample showed the highest crystallization and photocatalytic activity in degradation of Brilliant Red X3B (X3B) and Rhodamine B (RhB) dyes under visible light irradiation (λ > 420 nm). The increased visible-light photocatalytic activity of the prepared N-doped TiO2 nanorods is due to the synergistic effects of the enhanced crystallization, improved light-harvesting ability and reduced recombination rate of photo-generated electron-hole pairs. Note that the enhanced visible photocatalytic activity of N-dopednanorods is not based on the scarification of their UV photocatalytic activity.

The introduction of magnetism in SnTe-class topological crystalline insulators is a challenging subject with great importance in the quantum device applications. Based on the first-principles calculations, we have studied the defect energetics and magnetic properties of 3 d transition-metal (TM)-doped SnTe. We find that the doped TM atoms prefer to stay in the neutral states and have comparatively high formation energies, suggesting that the uniform TMdoping in SnTe with a higher concentration will be difficult unless clustering. In the dilute doping regime, all the magnetic TMatoms are in the high-spin states, indicating that the spin splitting energy of 3 d TM is stronger than the crystal splitting energy of the SnTe ligand. Importantly, Mn-doped SnTe has relatively low defect formation energy, largest local magnetic moment, and no defect levels in the bulk gap, suggesting that Mn is a promising magnetic dopant to realize the magnetic order for the theoretically-proposed large-Chern-number quantum anomalous Hall effect (QAHE) in SnTe.

The A-site calcium doped yttrium chromite was additionally doped with various transition metals on the B-site to improve the sintering, thermal behavior and electrical properties of these ceramics for future use as an interconnect material in high temperature solid oxide fuel cells (SOFC). With 10 % addition of Co, Cu, Ni, Fe, and Mn, the single phase orthorhombic perovskite structure remained stable over a wide range of oxygen partial pressures, as confirmed by X-ray diffraction. The substitution of Cu for chromium remarkably improved the sinterability and allowed full densification in air by sintering at 1400 degrees C. The substitution of Co and Ni significantly improved the electrical conductivity of yttrium chromites in both oxidizing and reducing environments. This was explained by the increase of charge carrier density with nickel and cobalt doping, as confirmed by Seebeck measurements. With 10% of nickel dopant, the electrical conductivity of Y0.8Ca0.2CrO3±δ increased from 12 to 38 S/cm in air and from 2 to 15 S/cm in reducing atmosphere at 950 degrees C. Mn doping had a negative effect on the sintering and electrical conductivity.

The magnetic properties of (ZnS)n clusters (n = 1 - 16) due to 3d transition metals have been investigated using spin polarized density functional theory. The transition metals are more stable at Zn site than at the S site in (ZnS)n clusters. The binding energy of (ZnS)n clusters increases significantly on doping with transition metal indicating enhanced structural stability of the doped (ZnS)n clusters. All 3d transition metals induced magnetic moment of order 5μB-1μB per atom in all (ZnS)n clusters. The magnetic moment is mainly localized on the TM dopant. The magnetic moment increases gradually with the increase in number of electrons in 3d orbital which is in accordance with Hund's rule till Mn and decreases thereafter. All 3d TMs retain their atomic magnetic moment in ZnS clusters of all sizes. Ti, V, Cr and Mn interact anti-ferromagnetically with the surrounding S and Zn, whereas Sc, Fe, Co, Ni and Cu interact with ferromagnetic interactions.

The formation of silver cluster structures at submicrometer spatial scales under the irradiation by high-power femtosecond laser pulses with high repetition rate was observed in various glasses containing silver ions. In order to account for the formation of these structures in metal-doped glasses, we present a theoretical model for the organization of noble metallic clusters induced by a train of femtosecond laser pulses. The model includes photoionization and laser heating of the sample, diffusion, kinetic reactions, and dissociation of metallic species. This model was applied to reproduce the formation of cluster structures in silver-doped phosphate glass. The parameters of the silver structures were obtained numerically under various incident pulse intensities and number of pulses. Numerical modeling shows that the involved microscopic physical and chemical processes naturally lead to the emergence of a silver cluster organization, together with charge migration and subsequent trapping giving rise to a strong static electric field buried in the irradiated area as experimentally observed. Based on this modeling, a theoretical basis is provided for the design of new metallic cluster structures with nanoscale size.

Metal-doped inorganic nanoparticles were synthesized for the multiplex detection of biomarkers by a sandwich-type inductively coupled plasma mass spectrometry (ICP-MS) immunoassay. The synthesized Cs-doped multicore magnetic nanoparticles (MMNPs) were used not only for magnetic extraction of targets but also for ratiometric measurement in ICP-MS. In addition, three different metal/dye-doped silica nanoparticles (SNPs) were synthesized as probes for multiplex detection: Y/RhBITC (rhodamine B isothiocyanate)-doped SNPs for CRP (cardiovascular disease), Cd/RhBITC-doped SNPs for AFP (tumor), and Au/5(6)-XRITC (X-rhodamine-5-(and-6)-isothiocyanate)-doped SNPs for NSE (heart disease). For quantification, the dopedmetals of SNPs were measured by ICP-MS and then the signal ratio to Cs of MMNPs was plotted with respect to the concentration of targets by a ratiometry. Limits of detection (LOD) of 0.35 ng/mL to 77 ng mL(-1) and recoveries of 83%-125% were obtained for serum samples spiked with the biomarkers. Since no sample treatment was necessary prior to the extraction, the proposed method provided short analysis time and convenience for the multiplex determination of biomarkers, which will be valuable for clinical application.

ZnO nanorods have been grown on indium-tin-oxide coated glass substrates by a low cost chemical process. Current-voltage characteristics have been studied using ZnO nanorods as photoanode in an electrochemical cell. The flat band voltage shift and depletion width of ZnO nanorods/electrolyte interface have been estimated from Mott-Schottky (MS) characteristics. The electrochemical impedance measurements have been carried out to study the charge transport mechanism at the semiconductor-electrolyte interface under dark and white light (100 mW/cm{sup 2}) illumination. The doping concentration of nanorods has been extracted from MS plot. Photoresponse behavior of ZnO nanorods is found to be enhanced than seed layers with the incident of white light. Spectral dependent photovoltage of ZnO nanorods has been carried out using monochromatic light of wavelength 250–600 nm. The photopotential recovery time has been estimated for nanorods and seed layers. The stability of ZnO nanorods as a photoanode has been investigated.

Metal-organic frameworks (MOFs) materials have aroused great research interest in different areas owing to their unique properties, such as high surface area, various composition, well-organized framework and controllable porous structure. Controllable fabrication of MOFs materials at macro-scale may be more promising for their large-scale practical applications. Here we report the synthesis of macro-scale Co-MOFs crystals using 1,3,5-benzenetricarboxylic acid (H3BTC) linker in the presence of Co2+, triethylamine (TEA) and nonanoic acid by a facile solvothermal reaction. Further, the as-fabricated Co-MOFs as precursor was pyrolytically treated at different temperatures in N2 atmosphere to obtain metallic Co nanoparticles embedded in N-doped porous carbon layers (denoted as Co@NPC). The results demonstrate that the Co-MOFs derived sample obtained at 900 °C (Co@NPC-900) shows a porous structure (including micropore and mesopore) with a surface area of 110.8 m2 g-1 and an N doping level of 1.62 at.% resulted from TEA in the pyrolysis process. As electrocatalyst, the Co@NPC-900 exhibits bifunctional electrocatalytic activities toward the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline media which are key reactions in some renewable energy technologies such as fuel cells and rechargeable metal-air batteries. The results indicate that the Co@NPC-900 can afford an onset potential of 1.50 V (vs. RHE) and a potential value of 1.61 V (vs. RHE) at a current density of 10 mA cm-2 for ORR and OER with high applicable stability, respectively. The efficient catalytic activity of Co@NPC-900 as bifunctional oxygen electrocatalyst can be ascribed to N doping and embedded metallic Co nanoparticles in carbon structure providing catalytic active sites and porous structure favourable for electrocatalysis-related mass transport.

The synthesis of RuO2 nanorods with reactive sputtering was demonstrated in this work. The synthesis process is very much like the metal organic chemical vapor deposition, except that RuO3 generated with reactive sputtering under high oxygen-to-argon flow ratio (>5SCCM /15SCCM) (SCCM denotes cubic centimeter per minute at STP) and high substrate temperature (>300°C) is used in place of the metal organic precursor. RuO2 nanorods tend to grow steadily with constant aspect ratio (˜27) and the field-emission characteristics appear very sensitive to their spatial distribution.

Super-plasticity and nano-scale surface roughness make thin film metallic glass (TFMG) a candidate for master mold of micro/nano imprint technique. Meanwhile, better mechanical properties of TFMG undoubtedly expand the life time of master mold. In this study, nitrogen is doped into Zr-based TFMG to exhibit the hardness higher than 10 GPa. Different from elements used to be doped into metallic glass, the role of nitrogen atoms plays in metallic glass is distinct and vital owing to its strong electronegativity. From the correlation of thermal and mechanical behavior, the role and effect of nitrogen in Ta-Zr-Cu-Al-Ag TFMG is discussed and proposed.

The effects of heavy rare earth (RE) additions on the Curie temperature (TC) and magnetocaloric effect of the Fe-RE-B-Nb (RE = Gd, Dy and Ho) bulk metallic glasses were studied. The type of dopping RE element and its concentration can easily tune TC in a large temperature range of 120 K without significantly decreasing the magnetic entropy change (ΔSM) and refrigerant capacity (RC) of the alloys. The observed values of ΔSM and RC of these alloys compare favorably with those of recently reported Fe-based metallic glasses with enhanced RC compared to Gd5Ge1.9Si2Fe0.1. The tunable TC and large glass-forming ability of these RE doped Fe-based bulk metallic glasses can be used in a wide temperature range with the final required shapes.